Carbonized wood and materials formed therefrom

ABSTRACT

A method of carbonizing cellulose-containing plants is disclosed. Wood is used as a precursor material which is carbonized under controlled temperature and atmosphere conditions to produce a porous carbon product having substantially the same cellular structure as the precursor wood. The porous carbonized wood may be used for various applications such as filters, or may be further processed to form carbon-polymer or carbon-carbon composites. The carbonized wood may also be converted to a ceramic such as silicon carbide. Additional processing may be used to form ceramic-metal or ceramic-ceramic composites.

CROSS REFERENCE TO RELATED APPLICATION

This is a division of U.S. application Ser. No. 08/678,084 filed Jul.11, 1996, now U.S. Pat. No. 6,051,096.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to carbonized plants, and moreparticularly relates to the fabrication of materials using wood andother naturally fibrous plants as precursor materials. The carbonizationprocess retains the anatomical features of the precursor plant whileconverting the composition of the plant to primarily carbon. Thecarbonized wood may then be formed to the desired shape. The shapedcarbon product may be used to form composites such as carbon-carbon andcarbon-polymer composites. The shaped carbon product may alternativelybe converted to ceramic compositions, or further processed to formceramic-containing composites such as ceramic-metal and ceramic-ceramiccomposites.

2. Background Information

Carbonization of wood for the manufacture of charcoal has been practicedsince the beginning of history. Destructive distillation was practicedby the ancient Chinese. The Egyptians, Greeks and Romans carbonized woodand distilled the volatiles for embalming purposes and the filling ofjoints in wooden ships. In ancient times wood charcoal was used for theremoval of odors, medicinal purposes, domestic cooking fuel, the makingof gunpowder and the refining of ores. The Industrial Revolution broughtabout a heavy demand for charcoal, especially for the making of iron. Upuntil the late 1800's the largest portion of manufactured wood charcoalwent into the reduction of iron ores. Today, coal derived cokes areused.

For many centuries charcoal was made in open air pits in the Westernworld. This entailed tightly piling bolts of air dried wood end to endforming a conical mound. This mound was then covered with several inchesof leaves, grass, needles, branches or moss depending upon what wasavailable. An additional few inches of dirt or sod then capped off themound. Openings were left at the base for air supply and up the centerto allow smoke to escape. The mound was then ignited at the base throughan opening. The mound tender made certain just enough air entered toallow a smoldering combustion which could take from one to several weeksto complete.

The production of wood charcoal became a major industry by the end ofthe nineteenth century. The conventional open pit methods wasted theby-product gasses that are released when wood is thermally decomposed.An entire industry was formed around the distillation of the vaporsevolved from wood carbonization. In the U.S. two branches of theindustry formed due to the fact that denser hardwoods give differentproducts than the lighter, more resinous softwoods. The products fromdestructive distillation of hardwoods included wood alcohol (methanol),acetate of lime and charcoal. The softwoods gave turpentine, tar, woodoils and charcoal. These products were made possible by carbonizing woodin a container designed such that the evolved gasses could be capturedand distilled.

The first development beyond the open pit method was the use of brickkilns designed to both contain the wood charge and provide a means totap into the exhaust. The brick kiln method meant a faster productionrate since mounds were not needed and rapid loading was possible. Thiswas also an asset for the iron industry which was rapidly expanding. Theheat needed for decomposition was obtained from the wood charge itself,just as in the open pit method. One drawback of the brick kiln was thata large portion of the evolved vapors were lost through the bricks, thusgiving limited yields.

The first high efficiency device for collecting carbonized wood vaporswas the small cylindrical retort made of cast iron or steel measuringsome 4 ft in diameter and 9 ft in length, capable of holding about twothirds of a cord. These were installed horizontally as pairs withbatteries of 10 or more pairs in long rows enclosed by brick. Heatingwas able to be provided externally from below the retorts and fuel wastypically in the form of charcoal, coal, wood gas, wood oil, wood tar orwood alone. A single run took about twenty four hours to complete. Thevapors were collected and distilled in the form of pyroligneous acidwhich was later refined to produce acetic acid, methanol, acetone,furfural, tars and oils.

The cylindrical retort evolved into a large rectangular steel retortenabling the use of cars for loading and unloading. A common size was 50ft long by 8 ft high and 6 ft wide. These retorts held more than tencords of wood and considerably increased production rates while reducingthe amount of labor involved. After a twenty four hour carbonizationcycle the cars were removed to cooling retorts and held for another oneor two days. Once removed from a cooling retort the cars were allowed tosit in the open for another two days thus giving a total time, from woodto marketable charcoal, of about ninety six hours. Some of the largerwood carbonization and distillation plants consumed as much as 200 cordsper day.

In the beginning of the twentieth century wood charcoal and itsdistillation products had fallen behind the products derived from coaland petroleum in several of the markets. Eventually, due to dwindlingsupplies of wood and the availability of higher grades of coals, themetallurgical market share became dominated by coal derived cokes. Thedemand for wood charcoal began to decline in the late 1800's. Petroleumbased products also began to take over some of the markets dominated bywood distillation products.

Currently in the U.S., the only significant markets for woodcarbonization products are activated carbons and charcoal briquettes.

Thermal degradation of wood has been studied with the intent of gaininginformation on its ignition characteristics. In the U.S. wood is used ona large scale in construction, especially for residential housing.Increased public concern over fire safety has prompted forest productindustries to investigate methods for eliminating or reducing theignition temperatures of wood and wood based products. The most commonapproach was chemical treatment to suppress various decompositionreactions. Progress in many cases was limited due to the potential forproduction of poisonous, or noxious fumes when products did finallyignite. Additional problems such as degradation of wood mechanicalproperties and bonding characteristics has hindered wide scalemanufacture of fire retardant products. In the 1980's construction gradefire resistant plywood entered the market and was widely installed asroof sheathing in many regions of the U.S. Unfortunately, the release tomarket was premature as the product suffered from ply delaminationresulting in product recall and much negative publicity.

Several U.S. patents address wood treatment methods. U.S. Pat. No.1,237,521 to Jennison discloses impregnating wood with preservativessuch as tar.

U.S. Pat. No. 1,483,733 to Kozelek discloses the production of wood formusical instruments by heating the wood in air to a temperature of from450 to 550° F. (232 to 288° C.). The heat treated wood, which has ayellow color, may then be treated with varnish prior to making themusical instrument.

U.S. Pat. No. 3,508,872 to Stuetz et al. discloses a process for theproduction of graphite fibrils using wood splinters less than 0.5 inchin length as a starting material. The splinters are first heated in airat 150 to 400° C., and are then charred at 2000 to 3000° C. Theresulting graphite fibrils are then incorporated in a binder to form acomposite.

U.S. Pat. No. 3,927,157 to Vasterling discloses the production ofcarbon-carbon composites using wood pulp as a starting material.Carbohydrate sugars are first chemically extracted from the wood,followed by heating the wood pulp at increasing temperatures of up to atleast 3800° F. The fibers are then mixed with a carbonizable binder andthe mixture is heated to form the carbon-carbon composite.

U.S. Pat. No. 4,170,668 to Lee et al. discloses a method forpre-charring the surface of wood in order to retard fire and rot.

U.S. Pat. No. 4,678,715 to Giebeler et al. discloses the impregnation ofwood with thermosetting polymers.

U.S. Pat. No. 5,143,748 to Ishikawa et al. discloses the surfacetreatment of wood with a plasma to impart water repellency.

The manufacture of graphite products is well known. Molded graphites areconventionally produced by a compaction process using a mixture ofcarbon filler with an organic binder which is heat treated to produceparts such as large electrodes used in metallurgical processes. In thelate 1800's, E. G. Acheson patented a process for manufacturing moldedgraphite parts which uses an electric resistance furnace for heattreatment of green products at temperatures adequate for graphitizationto occur (about 3000° C.). This was a significant development as itenabled carbon electrodes with relatively low resistivity to beproduced. Many improvements have since been made and the applicationsfor molded graphites has increased significantly since then. In the1940's, Enrico Fermi first used molded graphite as a moderator for aself sustaining nuclear reaction. Other modem applications of moldedgraphites include use as a refractory, electric motor brushes,electrical resistance heating elements in high temperature furnaces,rocket nose cones, rocket exit cones and various other aerospacecomponents.

Unlike molded graphites, glass-like carbons do not readily graphitizeand exhibit isotropic properties. Glass-like carbons are used as vesselsin chemical processing or analytical chemistry. They are also used ascrucible material for the melting of noble metals and special alloys,especially in dental technology. Glass-like carbons in the form of smallspheres are being considered for uses as catalyst supports. In addition,glass-like carbons are being produced in the form of open-cell foams.

Carbon foams are a fairly recent addition to the family of solid carbonmaterials. These are glass-like carbons produced in the form of an openpore foam. They are reported as having potential applications includingcatalyst supports, battery anodes, micro-porous membranes forfiltration, supercapacitor electrodes, low mass structural materials andcomposites.

There are several reported processes and precursors used to producecarbon foams, also referred to as reticulated carbons. A polymer whichis highly cross-linked and does not go through a fluid state is thefirst criteria for selecting a precursor. Some of the polymers of choiceare furfuryl alcohol, phenolics, polyacrylonitrile, polyurethane,resorcinol and others. In one process an inorganic is removed byleaching after carbonization, leaving a replica carbon which is thenfreeze-dried. Other carbon foams are produced by the blowing of bubblesinto a variety of liquid polymers.

Pyrolytic carbons and pyrolytic graphites are different in that they areproduced by chemical vapor deposition (CVD) from organic vapors. Theyalso differ from other forms of solid carbons in that the mainapplication is as a coating. Pyrolytic graphite was first produced inthe late nineteenth century and was used for lamp filaments. Althoughproduced as a coating, it can be made thick enough such that afterremoval from the substrate it has sufficient mechanical integrity tostay together. Some applications of these films, which vary in degree ofcrystallographic order, are heart valves and dental implants, coatingson molded graphite parts, coatings on fibers—especially ceramic fiberswhich are reactive with their composite matrix, coatings on opticalfibers for improved abrasion resistance and infiltration coating ofcarbon fiber preforms for the manufacture of carbon-carbon composites(also termed chemical vapor infiltration, CVI).

Carbon fibers have been produced using polyacrylonitrile (PAN) as aprecursor. Fibers of ultrahigh modulus having a modulus of elasticitygreater than 50% (>500 GPa) of the value of C₁₁ for graphite singlecrystals have been made.

During the 1970's progress was made in the use of pitch as a lessexpensive carbon fiber precursor. These precursors are capable ofproducing carbon fibers of ultra high modulus but, in general, of lowerstrength than those derived from PAN. The main difference between carbonfibers derived from pitch and those from PAN lies in the degree ofcrystallization and structural morphology of the solid carbon fibers. Ingeneral, PAN derived carbon fibers are non-graphitic while pitch derivedcarbon fibers are graphitic. While some present day applications utilizepitch based carbon fibers the majority of the market is taken by carbonfibers derived from PAN.

Carbon black and lampblack are forms of solid carbons produced bythermal decomposition of organics resulting in the formation of solidparticles in the gas phase. Their difference lies primarily in theorganic precursor and the size and atomic structure of the resultingsolid carbons. Lampblack is produced from the burning of oils, tars orresins in an oxygen limited environment. Carbon black is manufactured byincomplete combustion of a gas. Lampblack is one of the oldest forms ofmanufactured carbon, and the first known commercial process for makingnano-particles. It was made by collecting the smoke from an oil lamp.Lampblack is still used today as a black pigment in inks and paints.

Carbon black is produced by the channel process or the thermal process.In the channel process, small flames of natural gas impinge upon a coolmetal surface in the form of a channel, a rotating disk or a roller. Thecarbon powder forms on the cool surface and is then exposed to a hightemperature to oxidize the particle surface. The thermal process, alsotermed “cracking”, produces carbon black by thermal decomposition ofnatural gas in the oxygen free environment of a preheated chamber.Acetylene black is a special type of carbon black which is derived fromthe thermal decomposition of acetylene. Carbon black is usedcommercially in large quantities for the reinforcement of rubber in thetire industry.

Activated carbons are processed solid carbons with a highly developedporous structure and large internal specific surface area (>1000 m²/g).These processed solid carbons, which were developed as improvedadsorbents for the decolorization of sugar, can be produced by heattreatment in the presence of steam or carbon dioxide. An alternatemethod for producing activated carbon is to impregnate various vegetablematter with salts prior to carbonization. These processes are still usedtoday, with some modifications, for the production of activated carbonsfrom a diverse group of organic precursors.

It is known that the presence of certain metals or metallic compoundsduring heat treatment of a non-graphitic carbon can cause graphitizationto occur at temperatures well below what is otherwise required. It hasalso been established that non-graphitizable carbons may be transformedinto graphitic carbons by heat treatment with additions of metalliccompounds. This phenomenon has been given the name catalyzedgraphitization.

Solid carbon as a structural material finds many applications. Many ofthese applications make use of the refractory properties of solidcarbons. The combination of thermal stability, thermal shock resistanceand high strength and stiffness at very high temperatures make solidcarbon materials unique. One major disadvantage is their sensitivity tohigh temperature oxidation.

Monolithic carbon or carbon particulate composites are not reliably usedin structural applications due to their brittle mechanical behavior,flaw sensitivity, variable properties and difficulties in fabrication ofcomplex large components. Carbon fiber reinforced carbon matrixcomposites have been developed to overcome some of those limitations.Commonly referred to as carbon-carbon composites, these fiber reinforcedmaterials are now being used in some of the most severe environments.

Applications for carbon-carbon composites include rocket nozzles, rocketreentry heat shields, shuttle nose cone, brake pads and rotors inaircraft and race cars. Other applications include refractory molds anddies, high temperature engines, corrosion resistant structuralmaterials, heat exchanger tubes and biomaterials. Many applicationsutilize a three-dimensional reinforcement to achieve the propertiesdesired.

The properties of solid carbons with identical composition can varyconsiderably. The reinforcing phase is generally required to have highstiffness and strength. Conventional PAN based fibers meet theserequirements and are predominately used for both carbon-polymer andcarbon-carbon composites.

The matrix carbon phase is typically derived from the carbonization ofcross-linked polymers such as phenolics. These produce high carbonyields and a carbon phase which has distinctly different properties fromthe reinforcing fibers. The fiber-matrix bond is a critical factor indetermining the mechanical properties of the composite. If the bond istoo strong, crack deflection and fiber pull-out do not occur and thematerial exhibits little toughness.

Processing of carbon-carbon composites is typically accomplished by twodifferent methods, polymer impregnation followed by carbonization, orchemical vapor infiltration (CVI). CVI entails the use of a carbonaceousgas, such as methane, which is allowed to infiltrate a heated carbonfiber preform where it decomposes, leaving a carbon residue on fibersurfaces. Its disadvantage is that often pores become choked off leavingclosed porosity in the final composite. It also greatly increasesmanufacturing costs. Most commercial processes use polymerimpregnation/carbonization.

Preforms of woven carbon fibers are conventionally impregnated withpolymers by resin transfer molding techniques. Phenolics in an organicsolvent can fully penetrate the carbon fiber weave. After solventevaporation, phenolic carbonization is carried out. Yields of 60% aretypically obtained from phenolics. The first carbonization step resultsin a composite with considerable porosity and a second, and possiblythird, impregnation/carbonization sequence is necessary. Carbonizationmay be performed in a mold to limit distortion of the preform.

Another method for producing carbon-carbon composites is to start with apre-impregnated carbon fiber weave and form the desired shape.Carbonization, and additional impregnation/carbonization steps are thenperformed. Other polymers, pitch for example, are used as precursors toachieve different matrix properties.

Fiber reinforced polymer composites have found widespread use in recentyears. The largest market, by volume, is in the fabrication of boathulls. This market is dominated by glass fiber composites. Carbon fibercomposites are becoming less expensive and more competitive in someapplications. Much of the development of carbon reinforced polymers(CRP) has been supported by the aerospace and aviation industries wherespecific stiffness and specific strength are critical issues. Thisdevelopment has led to diverse use in applications ranging from sportsequipment to advanced aircraft components.

One of the advantages inherent in use of CRP's is that structures can bedesigned with a material tailored to the particular demands of theapplication. Composite properties can be made with varying degrees ofanisotropy so an exact fit of material property to structure can bemade. Complex shapes are also possible using composites since thestructure is formed at the same time the material is made. This is madepossible by use of several manufacturing approaches.

Manufacturing with carbon fiber composites is conventionally done bystacking woven or continuous fiber pre-pregs, by infiltrating mats orweaves with resins, by extrusion of chopped fibers mixed with polymersand by spraying fibers and resin into molds. Techniques have beenrefined such that composites of very high quality are becoming common inhigh performance applications. However, high performance composites areexpensive, partially as a result of the costs incurred in forming afinal product from the constituent materials. Stacking of pre-pregs isoften done by hand thus adding substantially to final product costs.Polymer infiltration often causes fiber swimming and shifting of weaves.Infiltration often results in considerable porosity in the finalproduct. These defects in composites severely limits their structuralworth in safety critical applications.

Ceramic materials are often processed by complex procedures to attain amaterial with properties specific to an application. Some of thoseproperties include high hardness, high stiffness and strength, corrosionresistance and a wide range of thermal and electrical properties.Ceramics are known for retaining these properties at high temperatures,making them useful in refractory applications. Silicates, oxides,nitrides and carbides are some of the fundamental ceramic materialsmanufactured today.

Many carbides are important industrial materials. These include calciumcarbide, iron carbide, silicon carbide, boron carbide, tungsten carbide,titanium carbide and niobium carbide. These are all synthetic industrialmaterials. Silicon carbide has received considerable attention for useas a high performance structural material where good strength andtoughness retention, oxidation and thermal shock resistance, and highthermal conductivity are demanded at temperatures approaching 1400° C.

Granular silicon carbide is manufactured by the Acheson process, thesame as is used for the production of molded graphite parts. In thisprocess, the green solid carbon, usually in the form of large cylinders,are laid out horizontally and packed in granular coke. The mound is thencovered with sand (silica). Large water cooled electrodes are fixed ateach end of the stack. High current is then passed through the stackwhich becomes self resistance heated. Temperatures of 2000-3000° C. aregenerated which graphitizes the solid carbon. At the same time areaction between the silica and coke packing produces silicon carbide.Traditionally the metallurgical, abrasive and refractory industries arethe largest users of silicon carbide. It has also been used forresistance heating elements, in electronic devices and in applicationswhere resistance to nuclear radiation is advantageous.

Traditional ceramic processes for making monolithic products involvesthe sintering, or densification, of ceramic powders by high temperatureheat treatment. This involves both surface and bulk diffusion mechanismsto attain full densification. Sintering results in shrinkage from thegreen state, making necessary the machining of a hard material whenclose tolerances are called for. Oxide ceramics are typically processedthis way.

Carbides and nitrides do not readily sinter due to limited diffusion inthe covalently bonded solids. Many industrial applications make use of ametallic phase which acts as a glue holding together carbide particles(cermets). Other processes for producing monoliths involve high pressuresintering (HIP) or reaction bonding of particles, e.g., reaction bondedsilicon nitride.

In some cases ceramic monoliths are manufactured directly fromprecursors without forming intermediate powders. Chemical vapordeposition is used for producing ceramic coatings. As another example,silicon carbide fibers are produced by pyrolysis of organometallicpolymer fiber precursors. The Yajima process entails the use ofpolysilane polymers which are thermolized to form carbosilane, a polymerwith a backbone of mostly alternating silicon and carbon atoms. Thecarbosilane is drawn into a fiber which is oxidized to promotecross-linking, then heat treated to approximately 1200° C. to form asilicon carbide fiber with a low degree of crystallinity. These fibers(Nicalon®) are used as reinforcements in high performance ceramiccomposites.

A relatively new approach for making monolithic ceramics of net shapeutilizes carbon foams as a precursor for the reaction conversion to acarbide. Silicon and silicon-refractory metal alloys are used as aninfiltrant to form a carbide by reaction at high temperatures. Dependingon the void volume of the precursor carbon foam, silicon carbidemonoliths with varying degrees of porosity or residual infiltrant havebeen produced with little or no bulk dimensional change. Porous siliconcarbide foam has been considered for high temperature filters andsurface combustion plates. It can also be used as a substrate to carrymaterials such as boron nitride used in semiconductor dopingapplications.

In summary, many different types of carbon-containing materials areknown. The carbonization of wood has been practiced for thousands ofyears. However, there is still a lack of disclosure of the use ofmonolithic structures made from carbonized wood. Specifically, nostudies have been found relating to methods by which relatively largepieces of wood can be carbonized while retaining their mechanicalintegrity. Further, no information relating to the production of largecrack-free charcoal has been reported. In addition, no study of thereduction in dimensions of wood as a result of carbonization has beendone. Measurement of resulting char mechanical properties can not befound in the literature. Furthermore, the successful production ofcomposite materials and ceramics based on carbonized wood having theoriginal structure of the precursor wood has not been achieved. Thepresent invention has been developed in view of the foregoing and otherdeficiencies of the prior art.

SUMMARY OF THE INVENTION

The process of the present invention involves the selection of anappropriate plant based on its composition and anatomical features. Theplant is treated under controlled atmosphere and temperature to yield aporous monolith of different composition from the biological precursor.In many applications, this monolith will be nearly all carbon, but maycontain other elements as well. The porous carbon monolith may then beformed to a final net shape depending on the particular application.

In one embodiment, the carbonized wood may be further converted to formvarious materials. For example, the porous carbon monolith may beimpregnated with a polymer to form a carbon-polymer composite. A highchar yielding polymer may be used with a second carbonization step toyield a carbon-carbon composite. Infiltration and reaction with moltenmetals can produce a net shaped carbide ceramic. Additional processingmay be used to produce ceramic-ceramic or ceramic reinforced metalcomposites. As another example, the carbonized wood may be infiltratedand reacted with metal oxides to convert the carbon to ceramic.

An object of the present invention is to provide a method of carbonizingwood while retaining its anatomical features. The method involves thetreatment of fibrous plant material under controlled atmosphere,pressure, and temperature conditions to convert the composition of theplant to carbon while maintaining the cellular structure of the plant.

Another object of the present invention is to provide a monolith ofcarbonized wood which is formed into a desired net shape.

A further object of the present invention is to provide a method ofmaking a carbon-polymer composite using carbonized wood as a precursor.

Another object of the present invention is to provide a carbon-carboncomposite by infiltrating carbonized wood with a carbon-forming materialsuch as high char forming polymer, and performing a second carbonizationstep to produce a carbon-carbon composite.

A further object of the present invention is to provide a method offorming ceramic materials from carbonized wood. Carbonized wood havingthe anatomical features of the precursor plant material may be reactedto form a porous ceramic structure. The pores may optionally be filledwith ceramic or metal material to yield ceramic-ceramic or ceramic-metalcomposites.

These and other objects of the present invention will become apparentfrom the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram illustrating various aspects of thepresent invention.

FIG. 2 is a partially schematic cross-sectional view of a piece of woodillustrating the longitudinal, radial and tangential directions,including an exploded portion showing directional planes of the wood.

FIG. 3 is a partially schematic illustration of different directionalplanes found in a typical piece of wood.

FIG. 4 is a schematic illustration of an apparatus used to carbonizewood in accordance with the present invention.

FIG. 5 is a schematic illustration of another apparatus used tocarbonize wood in accordance with the present invention.

FIG. 6 is a schematic illustration of a further apparatus used tocarbonize wood in accordance with the present invention.

FIG. 7 is a graph of weight and temperature difference versustemperature.

FIG. 8 is a graph of weight and temperature difference versustemperature.

FIG. 9 is a comparative photograph showing a carbonized wood samplehaving severe macrocracks in comparison with a crack-free sampleprepared in accordance with the present invention.

FIG. 10 is a photograph of various carbonized wood articles produced inaccordance with the present invention.

FIG. 11 is a photomicrograph showing the structure of a carbonized woodsample prepared in accordance with the present invention.

FIG. 12 is a photomicrograph showing the structure of a carbonized woodsample prepared in accordance with the present invention.

FIG. 13 is a photomicrograph showing the structure of a carbonized woodsample prepared in accordance with the present invention.

FIG. 14 is a photomicrograph showing the structure of a carbonized woodsample prepared in accordance with the present invention.

FIG. 15 is a graph illustrating reduction in dimension in the axial,radial and tangential directions for various species of wood.

FIG. 16 is a graph showing bulk density of carbonized wood versus bulkdensity of precursor wood for various species.

FIG. 17 is a graph of carbonized poplar yield versus heat treatmenttemperature.

FIG. 18 is a graph of reduction in dimension versus heat treatmenttemperature for a wood sample in the tangential, radial and axialdirections.

FIG. 19 is a graph of normalized density versus heat treatmenttemperature.

FIG. 20 is an X-ray diffraction plot of carbonized wood samples heatedto various temperatures showing graphitization at the highesttemperature.

FIG. 21 is a graph of stress versus strain for various carbonized andprecursor wood samples.

FIG. 22 is an X-ray diffraction plot of carbonized wood samples heatedto various temperatures showing graphitization at the highesttemperature.

FIG. 23 is a schematic illustration of a polymer impregnation apparatusin accordance with an embodiment of the present invention.

FIG. 24 is a radiograph of various carbon-polymer composites produced inaccordance with the present invention.

FIG. 25 is a photograph of a carbon-polymer composite produced inaccordance with an embodiment of the present invention.

FIG. 26 is a photomicrograph showing the structure of a carbon-polymercomposite of the present invention.

FIG. 27 is a photomicrograph showing the structure of a carbon-polymercomposite of the present invention.

FIG. 28 is a photomicrograph showing the structure of a carbon-polymercomposite of the present invention.

FIG. 29 is a photomicrograph showing the structure of a carbon-polymercomposite of the present invention.

FIG. 30 is a photomicrograph showing the structure of a carbon-polymercomposite produced in accordance with an embodiment of the presentinvention.

FIG. 31 is a photomicrograph showing the structure of a carbon-polymercomposite produced in accordance with an embodiment of the presentinvention.

FIG. 32 is a graph of stress versus strain for precursor wood,carbonized wood, carbon-epoxy composite and epoxy samples.

FIG. 33 is a photograph of a laminated carbon-polymer composite producedin accordance with an embodiment of the present invention.

FIG. 34 is a photograph of a laminated carbon-polymer composite producedin accordance with an embodiment of the present invention.

FIG. 35 is a photograph of carbon-carbon composites of the presentinvention.

FIG. 36 is an X-ray diffraction plot showing silicon carbide peaks forcarbonized wood samples which have been further treated with silicon.

FIG. 37 is an X-ray diffraction plot showing silicon carbide peaks forcarbonized wood samples which have been further treated with silicon.

FIG. 38 is an X-ray diffraction plot showing silicon carbide peaks forcarbonized wood samples which have been further treated with silicon.

FIG. 39 is an X-ray diffraction plot showing silicon carbide peaks forcarbonized wood samples which have been further treated with silicon.

FIG. 40 is an X-ray diffraction plot showing silicon carbide peaks forcarbonized wood samples which have been further treated with silicon.

FIG. 41 is a photomicrograph showing the structure of a porous ceramicmaterial derived from wood in accordance with an embodiment of thepresent invention.

FIG. 42 is a photomicrograph showing the structure of a porous ceramicmaterial derived from wood in accordance with an embodiment of thepresent invention.

FIG. 43 is a photograph showing a piece of ceramic material derived fromwood in accordance with an embodiment of the present invention.

FIG. 44 is a photograph of a ceramic-metal composite material producedin accordance with an embodiment of the present invention.

FIG. 45 is a photomicrograph of a ceramic-ceramic composite produced inaccordance with an embodiment of the present invention.

FIG. 46 is an X-ray diffraction plot for a silicon carbide samplederived from carbonized wood which has been further treated to convertresidual silicon to silicon nitride.

FIG. 47 is an X-ray diffraction plot for a silicon carbide samplederived from carbonized wood which has been further treated to convertresidual silicon to silicon nitride.

FIG. 48 is a photograph of a ceramic-containing composite produced inaccordance with an embodiment of the present invention.

FIG. 49 is a photograph of silicon carbide fibers and a silicon carbidetube derived from bamboo.

FIG. 50 is a graph of differential temperature versus temperature.

FIG. 51 is a photograph of carbonized fabric including a piece of fabricthat has been converted to ceramic after carbonization in accordancewith an embodiment of the present invention.

FIG. 52 is a photograph of carbonized wood samples derived from pressedwood including a sample that has been converted to ceramic after thecarbonization step.

FIG. 53 is an X-ray diffraction plot of carbonized wood samples havingsilicon carbide peaks.

FIG. 54 is an X-ray diffraction plot of carbonized wood samples havingsilicon carbide peaks.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

FIG. 1 schematically illustrates various aspects of the presentinvention. Wood or other cellulose-containing plants are carbonizedunder controlled conditions, with the carbonized product retainingsubstantially the same macrostructure as the precursor plant material.The carbonized product may then be formed to the desired shape byconventional working or cutting methods such as sawing, sanding,drilling, turning, milling, routing and the like. The shaped porouscarbon material may be used for various applications such as shapedactivated carbon, refractory insulation and high temperature filters.Alternatively, the shaped carbon monolith may be further processed toform carbon-containing composites including carbon-carbon andcarbon-polymer composites. Such composite materials may be used forapplications such as lightweight structures, furniture, brake shoes,sports equipment, high temperature tubing, brake rotors and the like.

In another embodiment, the shaped carbon monolith may be at leastpartially converted to a ceramic such as carbide or nitride. Theseceramic-containing materials substantially retain the porous cellularstructure of the carbonized wood. Such porous ceramic materials may beused for refractory insulation, abrasives, high temperature filters,etc.

In a further embodiment, the porous ceramic structure may be infiltratedwith various materials including metals and ceramics to providecomposite materials, for applications such as lightweight structures,cutting tools, armour, propellors, turbine blades and the like.

The present invention provides a novel processing approach for themanufacture of porous carbons, composites and ceramics using wood andother naturally fibrous plants as precursors. The process has thepotential for producing industrially important materials at a reducedcost due to its simplicity, and the fact that it makes use of arenewable resource.

In accordance with the present invention, “carbonized wood” means apredominantly carbon-containing material formed from wood or othersimilar cellular plant matter comprising at least 70 weight % carbon,preferably at least 80 weight % carbon. More preferably, the carbonizedwood comprises greater than about 90 weight % carbon, most preferablygreater than about 95 weight % carbon. Where the carbon is provided inthe form of graphite, the carbonized wood typically comprises about 99weight % carbon.

The carbonization process of the present invention typically results insubstantial weight loss of the wood precursor material. For kiln-driedwood having about 12 weight % water, the carbonization process typicallyresults in a weight loss of at least 40 weight %. Typical weight lossesrange from about 60 to about 80 weight % depending on the particularwood species. For many structural applications, a weight loss of about60 weight % is satisfactory, while for applications such as activatedcarbon, a weight loss of about 85 weight % is preferred.

The carbonization process of the present invention decomposes organicconstituents of the precursor wood to obtain carbon residue. Preferably,at least about 80% of the organic constituents comprising C—H bonds aredecomposed to carbon, more preferably at least 90 weight %. Mostpreferably, at least about 95 weight % of the organic constituents aredecomposed to carbon, with 99 weight % being particularly preferred.

In accordance with the present invention, “graphitization” means theconversion of carbon from a substantially amorphous structure to asubstantially crystalline structure, as identified by the occurrence ofthe 002 X-ray diffraction peak.

The following steps are used in accordance with a preferred embodimentof the invention. A suitable plant is carbonized under highly controlledconditions to obtain a solid carbon which retains substantially all ofthe anatomical features of the precursor. The plant precursor preferablycomprises virgin wood which has not been processed other than by kilndrying and cutting to shape. The carbonized wood is then shaped to thenet shape of the desired final product. Next, the shaped carbon may beconverted to a final product. Conversion may produce carbon-polymercomposites, carbon-carbon composites, ceramics and ceramic composites.Alternatively, the shaped carbonized material may be used withoutsubsequent conversion.

Carbon in the solid state has several polymorphs each with distinctcharacteristics. The guidelines of the International Committee forCharacterization and Terminology of Carbon (ICCTC) are used herein.Solid carbon as used herein includes glass-like carbon, non-graphiticcarbon, graphitic carbon, carbon fiber and others.

The polymorph of carbon termed graphite is anisotropic in nature due tothe mixed bonding of the structure and the crystal symmetry. There aretwo polytypes: hexagonal and rhombohedral. Natural graphites generallycontain more than 90% of the hexagonal form with the remainderrhombohedral. The hexagonal polytype is the thermodynamically stableform of graphite.

The carbon atoms in graphite have both σ- and π-bonding and form atwo-dimensional hexagonal lattice in the basal plane. These layers arestacked together with ABAB registry and bound by weak van der Waalsforces arising from the delocalized π-bonds. Within the basal planeatoms are bound by the covalent sp² hybrid (σ-) bond which gives thecrystal great stiffness and strength perpendicular to the c-axis. Alongthe c-axis stiffness and strength is low. The layers readily shear andcleave.

Electrical and thermal properties are also directionally dependent ingraphite. The delocalized electrons are capable of charge transport inthe basal plane but not perpendicular to it. Thus the electricalconductivity has a metallic character to it in the basal plane. Thermalconductivity is also high in the basal plane owing to the stiff covalentbonds. Thermal conductivity along the basal plane is about 200 timesgreater than perpendicular to it. When little phonon scattering occurs,as in a highly ordered single crystal, the thermal conductivity can beas high as 4180 W/mK along the basal plane.

Thermal expansion in graphite is also highly anisotropic. Unlike mostmetals, the thermal expansion is negative along the basal plane attemperatures up to 400° C. above which it becomes slightly positive. Inthe c-direction, however, thermal expansion is positive with acoefficient of 25×10⁻⁶/° C. at 0° C. This substantial anisotropy inthermal expansion can lead to high internal stresses with temperatureexcursions.

Other forms of solid carbon are composed of mostly elemental carbon as amixture of well ordered, but small, crystallites surrounded by lessordered regions. These crystallites may have two- or three-dimensionallong range order as determined by diffraction techniques. The degree ofcrystallographic order varies depending on precursor material andprocessing conditions. These solid carbons are either non-graphitic orgraphitic, the former being further grouped into graphitizable ornon-graphitizable categories. They may exhibit anisotropic properties orbe essentially isotropic.

The distinction between solid carbon and graphitic carbon is primarilymade on the basis of degree of crystallinity. Solid carbons, thoughcomprised of very small crystalline regions of graphitic nature, areeither amorphous, non-graphitic or graphitic when characterized by x-raydiffraction. The term solid carbon covers all natural and syntheticmaterials which are mainly comprised of the element carbon. Amorphouscarbons are those in which there is no long range order in the solidcarbon. Non-graphitic carbon has two-dimensional long range order.Graphitic carbons show three-dimensional long range crystallographicorder, albeit of varying degrees depending upon the material, andtherefore show distinct peaks when x-ray diffraction is used. Bothforms, non-graphitic and graphitic carbons, may have anisotropicproperties.

In accordance with the present invention, monolithic carbonized wood canbe produced without forming cracks usually associated with activatedcharcoal. As described more fully below, controlled atmosphere andheating rates produce thermal decomposition which avoids crackformation. Substantially all of the anatomical features of the precursorwood species are retained in the carbonized wood. The resulting solidcarbons are easily machined to exact dimensions using standard tools andprocedures.

The advantages of using carbonized wood as a precursor for compositesare realized when its directional morphology and properties areutilized. Unlike fiber reinforced materials, carbonized wood offers amonolithic porous structure for infiltration of a second phase. Thisstructure does not necessitate the use of molding for polymer or metaltransfer and eliminates the problems associated with fiber swimming. Thehighly aligned cells offer anisotropy of mechanical properties andpermeability. The natural porosity of the carbonized wood can be used toobtain uniform infiltration of a polymer. The porosity of the carbonizedwood can also be utilized for a solid carbon filter, adsorbent orcatalysis substrate. Furthermore, net-shape processing can be obtainedby shaping the carbonized wood to exact dimensions before converting toa composite.

In accordance with one embodiment, materials processing using carbonizedwood produces industrially important ceramics such as SiC, Si₃N₄, B₄C,AlN and the like. This method allows the production of advanced ceramicsof net shape. The process utilizes inexpensive precursors, eliminatesthe need for special handling and sintering of powders and minimizes themachining of a hard ceramic by allowing a carbonized solid material tobe shaped prior to conversion to the ceramic. A ceramic which retainsthe cellular features of the precursor wood may be produced. Forexample, a SiC micro-honeycomb ceramic may be produced which haspotential applications for high temperature filters or as a catalystsupport. Silicon carbide ceramics may also be produced which containresidual Si infiltrant. The resulting composite may optionally benitrided to form a ceramic/ceramic composite.

FIG. 2 is a partially schematic perspective view of a tree cross-sectionshowing the longitudinal or axial, tangential, and radial orientationsof the wood. The wood includes different directional planes, labelled aslongitudinal-radial (LR), longitudinal-tangential (LT) andradial-tangential (RT), as shown in the exploded view of FIG. 2.

FIG. 3 illustrates the cellular structure of a typical piece of wood inthe LR, LT and RT planes. The wood comprises longitudinal cells and raycells, as well as earlywood and latewood regions. The elongated cells ofthe precursor wood, as well as the cells of the carbonized wood producedin accordance with the present invention, typically have aspect ratiosof greater than 2 to 1, usually greater than 10 to 1 up to 100 to 1 andhigher.

Both hardwoods and softwoods are comprised of elongated tubular cellsaligned with the axis of the tree trunk as shown in FIGS. 2 and 3. Theseare referred to as longitudinal cells, fibers or tracheids. Thelongitudinal cells give the grain direction, which corresponds to thedirection in which most wood splits or cleaves. Longitudinal cells varyin length from one species to another but in general are longer insoftwoods than in hardwoods. Additional ray cells extend from the center(pith) of the trunk radially outward to the cambium layer. These raycells are therefore perpendicular to the longitudinal cells. There aremany more longitudinal cells than ray cells, the proportion variesbetween species. Softwood. ray cells on average occupy about 10% of thewood volume, hardwood ray cells about 20%.

Hardwoods differ in cellular structure from softwoods in several waysand in general tend to have a more complex anatomy. The most distinctfeature is that hardwoods typically contain fluid conducting pores(vessel elements) arranged parallel to the axis of the tree. Softwoodsdo not have these special pores but are capable of fluid conductionsolely via tracheids. The hardwoods are grouped into ring porous,diffuse porous and semi-ring porous depending upon the arrangement ofvessel elements. For example, in a ring porous wood such as red oak(Quercus rubra) the pores are closely packed in the inner portion of theearlywood giving that region very low bulk density. In diffuse porousbasswood (Tilia americana) the pores are evenly distributed throughoutan annual ring such that little variation in bulk density occurs as aresult of the vessel elements. Finally, an intermediate arrangement ofpores termed semi-ring porous is exemplified by butternut (Juglanscinerea).

The majority of mature wood cells are dead and hollow. The resultingtissue (secondary xylem) is composed of cell walls and voids (lumens).Typical softwoods by volume contain about 90% to 95% fibrous cells(fibers, tracheids or longitudinal cells). These cells are square torectangular in cross section, have closed tapering ends, and arearranged such that their ends overlap adjacent cells. They are alsoarranged in aligned radial rows. The widths of the fibers are generallyabout 35 to 50 microns. They are typically about 3 to 5 mm long givingan aspect ratio of about 100 (based on the hollow fiber). Rays arecomposed of brick-like, often living cells called parenchyma. Parenchymaare food storage cells that exist in hardwoods as well. These functionin radial fluid conduction and food storage, and frequently containextraneous materials such as starch, fats, oils, various sugars andinorganic deposits such as calcium oxalate crystals or silica. The raysof some species also contain cells called ray tracheids which aresimilar to parenchyma but are dead at maturity. Whether with tracheidsor not, rays are usually several cells high. In most softwoods they areonly one cell wide but can be several cells wide. A few softwood speciescontain a noticeable number of longitudinal parenchyma but this isuncommon.

Resin ducts are tube like voids in the xylem of some softwoods which areeither longitudinally or radially oriented. These ducts are lined withspecial parenchyma called epithelial cells that secrete oleoresin intothe duct. This anatomical feature is distinct to softwoods.

Hardwoods, as mentioned above, contain mostly fibers but also the muchwider cells called vessel elements. These cells, from about 0.02 to 0.5mm in length, are stacked endwise to form tubes (or pores). The ends ofall vessel segments ate perforate, or open, for free flow of liquidsbetween cells. In some species the segment ends are completely openwhile others contain a series of parallel cross bars (scalariform) orsome other design (reticulate). This morphology is different from woodfibers which are completely imperforate. Hardwood fibers occupy aproportionally smaller volume of wood tissue than softwood fibers due tothe presence of pores. The fibers are smaller in width by about one halfand length by about one third.

A variety of cell types are found in hardwoods. They can be classifiedwith respect to their orientation in the xylem. The cells verticallyoriented are fibers (libriform fibers, fiber tracheids and vasicentrictracheids), axial parenchyma and vessel elements. Those horizontallyoriented are ray parenchyma (procumbent cells and upright cells),homocellular rays and heterocellular rays. The parenchyma cell contentof hardwoods is on average much larger than that in softwoods. This is aresult of the wider rays (1 to 50 cells), greater ray volume and arelatively high proportion of longitudinal parenchyma. Also, the rays ofhardwoods are usually all parenchyma (i.e. no ray tracheids).

The wood tissue, including cells and intercellular material, is acomposite system composed of a variety of organic polymers. The basicstructural component of all wood cell walls is cellulose. It is a longchain linear polysaccharide (and carbohydrate) composed of glucose, asix carbon sugar (contains a hexagonal ring with 5 carbon and 1 oxygen).It has a general formula of (C₆H₁₀O₅)_(x). The glucose in celluloseaccounts for approximately 40-45% of the oven dry weight of wood tissue.

The cellulose superstructure has a matrix of lower molecular weightpolysaccharides that contain short side chains. These carbohydrates aremostly combinations of various five carbon sugars (xylose and arabinose)and six carbon sugars (glucose, mannose and galactose). Thosecarbohydrates are different from cellulose in structure and molecularweight but have enough similarities to be called hemicelluloses.Together, the carbohydrates of cellulose and hemicellulose compriseabout 65% to 75% of the dry wood.

The third major component of the wood tissue is lignin which comprisesabout 18% to 35% of the dry wood. It is a three dimensional, highlybranched polyphenolic molecule of complex structure and high molecularweight. It permeates cell walls and intercellular regions (middlelamella) giving the wood its relatively high hardness and rigidity. Themiddle lamella region is typically about 70-80% lignin by weight. Itacts as a glue which bonds together all wood cells. Even though themiddle lamella has a very high lignin content, the cell walls usuallycontain about 70% of the total lignin in the wood due to their highvolume fraction.

Proportions of the three major components of wood varies from tree totree and between species. In general, softwoods contain a higherproportion of lignin than do hardwoods.

During the early stages of wood cell growth the cell wall is thin anddeformable. This early wall, termed the primary wall, is typically addedto near the end of cell growth by a secondary wall manufactured on thelumen side. Wood fibers, vessels and certain other elements thatfunction in passive conduction and/or support typically develop asecondary wall.

The cellulose polymer comprises about 40 to 50 wt % of dry wood and ispartially crystalline. The crystalline regions have a space groupsymmetry of P2₁, with parameters of a=16.34, b=15.72, c=10.38 Á, andgamma=97.0°. A unit cell contains eight cellibiose moieties and themolecular chains pack in layers which are held together by van derWaals' bonds. The cellulose molecules are unbranched chains with8-10,000 glucose residues in a typical wood. There is considerablemolecular weight distribution and variation between species andindividuals.

In the mature cell, partially crystalline cellulose is aggregated intolarger structural units called elementary fibrils which, in turn, formthreadlike aggregates known as microfibrils which aggregate intomacrofibrils. The microfibrils combine to form sheets of the cell wallwhich ultimately laminate to form discrete wall layers. In the primarywall the cellulose microfibrils form a layer with a random interwovennetwork. At the secondary wall the microfibrils tend to be aligned aboutthe fiber axis in a helical fashion at a specific angle (microfibrilangle) with respect to the fiber axis. There are three distinguishablelayers in the secondary wall each with a specific average microfibrilangle (average of several lamella of different orientation). Theoutermost layer is very thin (about 0.1-0.2 micron) and has an averagemicrofibril angle of about 50° to 70°. The next layer forms the bulk ofthe secondary wall and is several microns thick. The average microfibrilangle is relatively small, usually about 50° to 20°. This layercontributes significantly to the mechanical properties of the woodparallel to the grain. The alignment of microfibrils results in apreferred orientation of cellulose crystallites detectable by x-raydiffraction analysis. The layer closest to the lumen is generallysimilar to the outermost layer except that it is a little thinner andhas an average sublamella microfibril angle of about 60° to 90°.

Both softwood and hardwood fibers have closed ends but small openings inthe cell walls allow for fluid conduction from one fiber to another,from fiber to vessel elements, and from fibers to rays. These smallvoids, termed pits, in the secondary wall occur in adjacent cellsopposite from one another forming a pit pair. The pit pairs areseparated by a pit membrane which is a remnant of the original primarywalls of the cells before the secondary walls were added. This membranemay be either porous (as in softwoods) or nonporous as is generallyfound in hardwoods. When it is nonporous, fluids must rely upondiffusion to move through the pit from one cell to an adjacent cellrather than by free liquid transport. When a pit appears as a plug ofmaterial removed from the cell wall it is called a simple pit. If, onthe other hand, the pit has a more elaborate, domelike shape, it iscalled a bordered pit. Different types of cells typically contain one orthe other type of pit. The pits also are arranged in specific patternson the cell walls and can be used as an identification aid for aparticular wood species.

A consequence of the hydrophilic nature of wood is that it will seek tomaintain an equilibrium moisture content with the surroundingatmosphere. If sufficient moisture exists, the cell walls swell until asaturation state is reached. This moisture content is called the fibersaturation point. Loss of water from this saturation point (fromdiffusion and evaporation) results in cell wall shrinkage whichtranslates to bulk wood shrinkage. When the tree is living, the lumensof the wood are generally filled with fluid. Thus, the loss of this freewater upon the cutting of the tree does not contribute to shrinkage ofthe wood. That occurs only because of the loss of water below the fibersaturation point.

Extraneous materials are present in most woods (typically about 5 to 10wt %) that do not contribute to its structure. Various complex organicchemicals, called extractives, are found which can be removed from thewood by use of solvents. The amount of extractives varies from about4-10 wt % (up to 20 wt % in unusual cases) depending on species andgrowing conditions, and can include gums, resins, tannins, oils andstarch. They can serve various functions such as intermediates in treemetabolism, defense against microbial attack and food reserves. Theseorganics can impart color, odor and decay resistance to the wood.

Other extraneous materials found are minerals which are drawn from thesoil. Elemental analysis has identified calcium, potassium, magnesium,sodium and manganese. Anions include, silicates, carbonates, phosphatesand sulfates. The most often found inclusions are calcium crystals orsilica grains. Though they are found in some softwoods, crystalsnormally occur in hardwoods, especially those of tropical origin. Themost common are calcium oxalate, but calcium carbonate and calciumphosphate have also been found. Grains of silica are found in manytropical hardwoods and are often responsible for the dulling of cuttingtools.

There are many different chemical constituents that form the materialreferred to as wood. Most, by weight, are of organic nature. If oneexcludes the minor amounts of minerals and trace metal ions, dry woodhas an elemental content of about 50 wt % carbon, about 44 wt % oxygenand about 6 wt % hydrogen.

Some extremes exist in the plant kingdom as far as composition isconcerned. One genus, Equisetum, is a remnant of primitive vascularplants which is characterized by jointed hollow stems. The stems arelined with ridges which are rough to the touch due to a covering ofsmall tubercles of a siliceous material. Equisetum, also known asscouring rush, was used by pioneers for the washing of pots and pans.The content of siliceous compounds can be considerably high in suchplants.

Wood properties are of considerable importance in the process ofselecting a particular piece for a specific application. This may entailchoosing between different species based upon properties such asdensity, stiffness, strength, hardness, permeability, decay resistance,workability, availability or cost.

The composite material which comprises wood has a true density ofapproximately 1.5 g/cm³. On the other hand, the average bulk density ofwood ranges from about 0.16 g/cm³ for balsa (Ochroma pyramidale) toabout 1.14 g/cm³ for lignum vitae (Guaiacum spp.). A species with a bulkdensity of 0.5 g/cm³ (a typical density for many species) is therefore66% void by volume. The bulk density is quite variable within a speciesowing to both variations in moisture content and the ratio of earlywoodto latewood. Also a contributing factor is the ratio of heartwood tosapwood. All other factors being constant, the bulk density of wood isdependent upon cellular diameters and wall thickness. For example balsahas very large fibers with thin walls which is contrasted by northernred oak (Quercus rubra) which has fibers of small diameter and verylittle void space in the lumen.

The wood precursors used in accordance with the preferred embodiment ofthe present invention are cut from the desired species of tree anddried. Kiln drying is particularly suitable. The dried wood is then cutto shape, allowing for shrinkage during the carbonization process. Thewood may be cut to any desired shape. For example, the wood may be cutinto pieces having lengths of greater than about 1 inch. Such pieces mayhave widths of at least about 0.5 inch, and may have heights of at leastabout 0.1, 0.25, 0.5 inch or greater. In many cases, the piece of woodextends at least about 0.5 inch in at least two of the L-R, L-T and R-Tplanes. As a particular example, the piece of wood may extend at leastabout 0.5 inch in each of the L-R, L-T and R-T planes. The precursorwood pieces used in accordance with the present invention may have anysuitable maximum size depending on the desired end use. Thus, relativelylarge blocks, sheets, strips, rods and other shapes may be carbonizedaccording to the present method.

After the appropriate size and shape has been selected, the piece ofwood is preferably heated in an inert atmosphere to achievecarbonization. The inert atmosphere is preferably non-oxidizing, e.g.,containing less than 5 volume % O₂ gas, preferably less than 1 volume %and more preferably less than 1000 ppm O₂ gas. Suitable non-oxidizingatmospheres include vacuums, inert gases and noble gases. Nitrogen is aparticularly preferred non-oxidizing medium. The piece of wood may beheated at subatmospheric, atmospheric and superatmospheric pressures,and combinations thereof. The use of substantially atmospheric pressureis suitable for many operations.

The piece of wood is heated in the substantially non-oxidizingatmosphere to a sufficient temperature at a sufficiently slow heat-uprate to carbonize the wood while substantially maintaining the cellularstructure of the precursor wood. The piece of wood is preferably heatedto a temperature of at least about 300° C. up to a temperature of about1500° C. or higher. Where graphitization is desired, temperatures of atleast about 2000° C. may be used. However, in one embodiment,graphitization catalysts may be used to reduce the temperature requiredfor graphitization to less than about 2000° C. as more fully describedbelow. Heating to a temperature of from about 400 to about 1000° C. isparticularly suitable for achieving carbonization of most wood pieces.Maximum temperatures of from about 500 to about 700° C. typicallyachieve the desired degree of carbonization without the necessity ofreaching extremely high temperatures.

During the heating process, sufficiently slow heat-up rates are used toavoid macro cracking of the wood and to maintain its cellular structure.Heat-up rates of less than about 20° C./hour are preferred, particularlybetween the temperatures of about 200 and about 400° C. In accordancewith the present invention, a sufficiently slow heat-up rate between thetemperatures of 200 and 400° C. has been found to produce the desiredcellular structure in the resultant carbonized wood. The heat-up rate ispreferably from about 1 to about 10° C./hour between the temperatures of200 and 400° C. Heat-up rates of from about 2 to about 5° C./hour areparticularly suitable within this temperature range. After a temperatureof about 400° C. has been reached, heat-up rates of less than about 20°C./hour are preferred. For example, where a piece of wood is heated to amaximum temperature of from about 500 to about 1000° C., it ispreferably heated at a rate of less than about 20° C./hour between thetemperature of about 400° C. and the maximum temperature.

The piece of wood may be heated to an initial temperature of from about50 to about 100° C. for at least about 0.5 hour to dry the wood prior tocarbonization. Thus, while kiln-dried wood of relatively low moisturecontent may be used as the wood precursor, it may be dried further atelevated temperatures prior to heating to the carbonization temperatureof at least about 400° C., for example.

The carbonized wood may be at least partially converted to graphite byheating to high temperatures of at least about 2000° C., typically 2500°C. Alternatively, in accordance with an embodiment of the presentinvention, the precursor wood may incorporate a graphitization catalystwhich facilities conversion of the carbonized wood to graphite at lowertemperatures, e.g., less than about 2000° C. Preferred graphitizationcatalysts comprise elements such as Cr, Cu, Ni, B, Ti, Zr and Fe. Forexample, the precursor wood may be treated with a wood preservativecomprising at least one of these elements which acts as a graphitizationcatalyst. A suitable wood preservative comprises copper chrome arsenatewhich, when impregnated into the wood prior to the present heattreatment process, reduces the temperature required for graphitization.

Upon carbonization, the piece of wood may undergo various degrees ofshrinkage. For example, some wood species may shrink from about 20 toabout 25% in the axial direction upon carbonization. Shrinkage of fromabout 20 to about 35% in the radial direction and from about 20 to about40% in the tangential direction is typical.

Various cooling rates may be used in accordance with the presentinvention to reduce the temperature of the carbonized wood. Coolingrates of less than about 100° C./hour may be used. However, for someapplications such as activated carbon, cooling rates of greater thanabout 100° C./hour may be utilized.

After the carbonized wood has been cooled, it may be shaped byconventional wood-working techniques. For example, the carbonized woodmay be cut by processes such as sawing, drilling, routing, milling,turning, grinding, sanding and the like.

In one aspect of the present invention, the pores of the carbonized woodmay be at least partially filled with materials such as metals,polymers, carbon and ceramics. Suitable metals include magnesium andother metals which do not adversely react with the carbon cellularstructure. Suitable polymers include thermosetting resins andthermoplastic resins such as phenolformaldehyde, polyetheretherketone(PEEK), polytetrafluoroethylene, polymethylmethacrylate (PMMA), and thelike. Epoxies, phenolics and pitch are particularly suitable polymersfor at least partially filling the voids of the carbonized wood. Wherethe polymer is subsequently converted to carbon to form a carbon-carboncomposite, phenolic resin polymers may be preferred.

In an alternative embodiment, the carbonized wood may be at leastpartially converted to a ceramic such as silicon carbide. The ceramicsubstantially retains the cellular structure of the precursor wood,including its porous structure. The pores of the ceramic material mayoptionally be at least partially filled with a metal. Alternatively, thepores of the ceramic may be at least partially filled with a ceramicmaterial. For example, the pores of a silicon carbide material may befilled with residual silicon, which is converted to silicon nitride byreaction with nitrogen.

A variety of wood species were selected for processing in accordancewith the present invention. These were cut to various sizes andthermally treated in one of several furnaces. The objective was toproduce monolithic pieces of carbonized wood, substantially free fromthe cracks normally associated with wood charcoal. Characterization ofthe resulting materials was done by measurement of length changes, bulkdensity, helium density, acoustic velocity, mechanical properties andcrystallinity by x-ray diffraction. Thermal analysis by DTA/TGA was alsoperformed. In addition to producing monolithic carbonized wood,conversion to composites and ceramics was also performed.

The wood chosen for this work was obtained from a specialty lumbersupplier and was selected based on straightness of grain, and absence ofknots or decay. All pieces were room dry (approximately 12%) andvisually crack-free. Where possible, boards thicker than 3.8 cm wereused, but dimensions differed among various species. Samples were cutfrom these boards with a 25 cm power miter saw equipped with a smoothcutting carbide-tipped combination blade. When wood cubes were made fortesting, the grain was oriented such that the cube faces corresponded tothe LR, LT and RT planes, as shown in FIGS. 2 and 3. Wood with littlecurvature or variation in growth rings was also selected for the cubes.A list of some of the wood species used in accordance with the presentinvention is provided at Table 1.

TABLE 1 Latin and Common Names of Wood Species Latin Name Common NameAcer saccharum maple, hard maple, sugar maple, bird's-eye maple Guaiacumspp. lignum vitae Juniperus virginiana Eastern redcedar Liriodendrontulipifera poplar, tulip poplar Nyssa sylvatica black tupelo Ochromapyramidale balsa Pinus spp. Southern yellow pine, yellow pine Pinusstrobus Eastern white pine, white pine, pine Quercus alba white oakQuercus rubra Northern red oak, red oak Sequoia sempervirens redwoodSwietenia spp. mahogany, Central American mahogany Tectona grandis teakTilia americana basswood, American basswood

Three different furnaces were utilized. The furnace used in many of thecarbonization runs was a Rapid Temp 1218 FL manufactured by CM Inc. Itwas equipped with an Inconel retort 21 cm wide and high by 42 cm deep.The polymer gasket used to seal the retort door was cooled by a waterjacket. Ports allowed for inert gas flow into the sealed retort. Theoutlet port was connected to a copper tube which passed into a series oftwo beakers (usually partly filled with water so that bubbling indicatedgas flow through retort) to distill some of the evolved vapors beforebeing sent to a laboratory vent. A nitrogen gas cylinder equipped with apressure regulator served as gas supply and was metered by a calibratedrotameter. A flow rate of 0.5 L/min was used in most examples. Retortpressure was maintained at, or slightly above, ambient. The furnacecontroller allowed for temperature ramp and dwell settings. The maximumoperating temperature of this furnace (referred to as “retort furnace”)was 1200° C. FIG. 4 is a schematic illustration of this setup.

The second furnace used had a maximum temperature of 1600° C. It was aRapid Temp tube furnace (model 830426) equipped with either an aluminaor mullite ceramic tube (referred to as “tube furnace”). The tubediameter was 5.8 cm with a furnace length of 70 cm and a hot zone 16 cmlong. Tube ends were sealed with rubber stoppers with through holes forcopper tubing. Stoppers were held in place with springs. Ceramic feltinsulation was placed just inside the ceramic tubes to prevent therubber from overheating. This insulation was porous so that gas flowcould be maintained. On the outlet end of the tube furnace vapors werepassed through Tygon tubing to a bubbler beaker to indicate gas flow.Inert gas was supplied to the inlet end of the furnace tube by regulatorequipped cylinders. Gas flow was controlled by a calibrated rotameter.Tube pressure was maintained at, or slightly above, ambient. For thisfurnace molydisilicide resistance heating elements were energized by aphase-angle fired SCR without current limiting. Because of this, heatingrates had to be kept to a minimum to avoid overcurrent to the elements.Slow heating rates (240° C./hr) were also used to prevent thermal shockof the ceramic tubes. Furnace controller allowed multiple temperatureramps and dwells. FIG. 5 is a schematic illustration of the tubefurnace.

The third furnace used was an Astro Industries Group 1000 GraphiteElement Furnace (referred to as “graphite furnace”). The maximumtemperature was 2500° C. which was attained by graphite resistanceelements. This furnace had a hot zone of 11.4 cm diameter and 12 cmhigh, and was gas fed by a rotameter and outlet vented to laboratoryexhaust. Vacuum capability allowed for evacuation of air prior toheating which was typically performed in nitrogen at, or slightly above,ambient pressure. The temperature was manually controlled by adjustmentof element power. Temperature was measured with either agraphite/graphite-boron thermocouple or a two-color pyrometer (IrconModline type R-99005). The upper end of the temperature range of thethermocouple was 2000° C., and the pyrometer, 2200° C. Pyrometerreadings of 2500° C. were observed and considered to represent thetarget temperature within 50° C. FIG. 6 schematically illustrates thegraphite furnace setup.

Helium density measurements were performed by weighing the sample mass(0.1 mg resolution) and then using a pycnometer for determining openpore volume. A stereopycnometer (Quantachrome Corporation) was employedwith helium gas supply at 18 psig. An attached mechanical vacuum pumpenabled samples to be degassed prior to volume measurement. Volumemeasurements were performed at ambient temperature, and a high pressureof approximately 18.0 psig and low of 0.0 psig. Samples were typicallymeasured whole and after grinding with mortar and pestle. Measurementsof lump silicon and graphite flakes gave results which were close totheir theoretical densities.

Bulk density was done by measuring sample mass, and dividing by volumedetermined from dimensions measured with micrometer (0.0005 inchresolution). Samples were measured before and after carbonization toobtain shrinkage data. Wood was measured at room dry conditions(approximately 12%).

Ultrasonic velocity was measured by contact methods. The equipmentconsisted of a Panametrics 5055 PR spike pulser/receiver and a HewlittPackard model 1743A 100 MHz two channel analog oscilloscope equippedwith a delta time function. Two compressional wave resonance transducerswith center frequencies of 1.0 MHz and diameters of 1.25 cm were used(Ultran WC50-1). Coupling to specimen was through either a liquid(Sonotech) or a polymer film (Parafilm). The through transmissiontechnique allowed for adequate signal to noise in the attenuativesamples (especially in transverse direction). Time of flight wasmeasured by overlapping the first significant break in the receivedsignal with the zero (in time) reference point on the transmittingsignal. The zero reference point was established by putting thetransducers in contact and observing the resulting change in thetransmitting transducer signal. The point where the transmitting signalfirst indicated a change was used for the zero time reference. Theaccuracy of this technique for time of flight values was found to besatisfactory.

Thermal analysis was performed on sawdust obtained from scraping woodspecimens (other powders were also analyzed). A TA Instruments SDT 2960simultaneous DTA-TGA was used with inert gas flow monitored by acalibrated rotameter. Sample cups used were either of platinum oralumina, depending on the temperature of the particular test. Gas flowrates and temperature ramp rates were chosen for each specific test.

Crystal phase identification was conducted by conventional x-raydiffraction techniques. Samples were either ground or scanned whole. Theequipment used consisted of a GE goniometer, an x-ray tube fitted with acopper anode, and a Diano Corporation generator control, amplifier, andpulse height selector. X-ray bandwidth was reduced by filtering with anickel foil. The system had a computer controlled upgrade package fromMaterials Data Incorporated. It consisted of a Databox microprocessorwhich controlled goniometer movement, and collected x-ray intensitydata. The intensity versus 20 data was down-loaded to a PC for analysis.Jade software, also from Materials Data Inc., was used to match thediffraction scans to files (powder diffraction file, PDF) on a compactdisc assembled by the International Center for Diffraction Data (ICDD).

Mechanical testing was done on an MTS 810 load frame in a manner similarto that used for compression testing of thick carbon/epoxy laminates.Specimens were cut to approximately 25 cm in cross-section and 76 cmhigh. Load was applied parallel to the axial direction of the wood andcarbonized wood. Scanning electron and optical microscopies, and x-rayradiography were used for assessing microstructure and uniformity ofimpregnation, respectively.

Thermal analysis was performed on several wood species and, in general,little difference in the data was found. Pure regenerated cellulosepowder (Aldrich Chemical #31,069-7) was analyzed as a reference for theanalysis of wood. The weight and differential temperature are plottedagainst temperature in FIG. 7. Initial weight loss and endotherm below100° C. results from loss of moisture. At approximately 300° C. thecellulose begins to decompose and loose considerable weight in anendothermic reaction. The carbonization is essentially complete by 400°C. with a corresponding 80% weight loss. Further heat treatment to 1000°C. results in an additional 6% weight loss (14% carbon yield). Thesmooth trough-like endotherm, and lack of discontinuities in the weightloss, is typical for polymers decomposing in a continuous reaction (atan even rate).

Wood carbonization proceeds through a series of overlappingdecomposition reactions. A typical DTA/TGA example is given in FIG. 8for the carbonization of lignum vitae. An initial weight loss andendotherm corresponds to loss of adsorbed water. Polymer decompositionis indicated by weight loss beginning under 200° C. and is likely thehemicellulose component of the wood. The rate of change in weight lossrapidly rises above 200° C. until approximately 275° C. where areduction of this rate is found. Presumably, the hemicellulosedecomposed in this temperature range. Above 275° C. the rate of changein weight loss again increases and reaches a maximum at 360° C. Here thecellulose has largely decomposed and the lignin components continue tobreak down. By 400° C. there is a 70% loss in weight and the wood isessentially decomposed. Further heat treatment to 800° C. gives a 21%yield of solid carbon.

All other species analyzed gave similar results, although some variationin yield was detected. Those examples performed with slower furnace ramprates gave higher yields than those performed at higher ramp rates.There was also some small variation in yield between different speciescarbonized with similar ramp rates. More quantitative informationconcerning solid carbon yields was collected by weight measurements ofmonolithic samples; as discussed below.

The effect of heating rate on monolithic pieces of wood can have aneffect on the integrity of the final product. Conventional wood charcoalis broken and cracked due to shrinkage stresses developed from thesurface of the material decomposing faster than its interior. This oftenresults when heating rates are too high for a uniform temperature to bemaintained in the decomposing wood. Each species will require specificheating rates based on both its density, permeability and thickness.Permeability in this case refers to the mass transfer of gases throughthe wood. If permeability is very low, by-product gasses build uppressure causing stress within the monolith and alteration ofdecomposition mechanisms, which may lead to cracking. To illustrate theeffect of improper carbonization conditions the following example isgiven.

A piece of white oak measuring 5×10×15 cm (radial, tangential, axial)was placed in the retort furnace packed with a layer of about 1 cm ofsawdust on all sides to promote uniform heating. The furnace wasprogrammed for a temperature ramp rate of 20° C./hr, up to 500° C. Thefurnace then cooled at 100° C./hr to ambient temperature. The specimenturned out cracked on all sides. Other specimens of basswood, teak,Honduran mahogany, and bird's-eye maple which were cut to similardimensions and carbonized in the same experiment came out intact andcrack-free. It is believed that the abundant tyloses found in white oakwhich render the heartwood impermeable, also influence the rate at whichdecomposition vapors escape. This causes pressure buildup, which in turnchanges the rate of decomposition of the wood interior causing internalstresses. These internal stresses then lead to cracking of thecarbonized wood.

A second piece of white oak from the same board was cut and packed inthe furnace in the same manner as the first. A ramp rate of 5° C./hr wasused but all other parameters were the same as the first run. Thespecimen produced was crack-free. A photograph of both specimens isshown in FIG. 9 with the cracked specimen on the left side.

Other large specimens were carbonized by selecting a sequence oftemperature ramp and hold segments. The following is the heatingschedule used for most of the large pieces:

1) 60° C./hr to 85° C., hold for 2 hrs to thoroughly dry the wood;

2) 5° C./hr to 200° C.;

3) 3° C./hr to 400° C.;

4) 10° C./hr to 600° C.;

5) 50° C./hr to room temperature.

The following wood specimens were carbonized using this schedule with anitrogen flow rate of 0.5 L/min: red oak (3.5×8×37 cm); basswood(4.7×6.7×37 cm); black tupelo (6.25×20×20 cm); bird's eye maple(3.3×8×15 cm); bamboo (40 cm long by 2 cm diameter).

All of these specimens turned out crack-free. Variation of dimensions insome specimens resulted from non-uniform shrinkage due to theorientation of grain. The result was a limited amount of warpage andtwisting. The specimens Were then machined to uniform dimensions on amachinist's mill fitted with a ceramic grinding wheel. Some of these areshown in FIG. 10.

Most of the carbonized specimens were of uniform, straight grain. Oneexample was performed on Eastern red cedar which contained live, orintergrown, knots. Specimens 2×12×12 cm were packed in sawdust andcarbonized with a slightly faster heating rate than described above(100° C./hr to 90° C., hold 3 hrs, 10° C./hr to 200° C., 5° C./hr to400° C., 15° C./hr to 600° C., cool 100° C./hr to ambient). Thesespecimens turned out crack-free, but with some warping. The knots andthe wood grain around them carbonized without visual signs of cracks.This indicates that a large-scale heterogeneity does not necessarilydestroy the integrity of the wood during carbonization.

Scanning electron microscopy was used in order to give the depth offield or contrast needed to fully investigate the morphology of theanatomical features. The specimens to be examined were heat treated to900° C. to increase electrical conductivity and thus avoid charging bythe electron beam. Many species and orientations were observed in thismanner. The specimens were prepared by scoring a surface, followed byapplying pressure or impact to the opposite side. This method created aslightly rough and non-planar surface. When examined, all anatomicalfeatures of the species were identified and found to be intact, withoutany evidence of macrocracking. The observations confirmed thatcarbonization of wood results in a solid carbon material which retainsall of the anatomical features of the precursor. Photomicrographs of arepresentative group of these porous carbons are shown in FIGS. 11-14.FIG. 11 is carbonized balsa wood, while FIG. 12 is carbonized basswood.FIGS. 13. and 14 are carbonized redwood and carbonized red oak,respectively.

Carbonization of a set of seven species representing a wide range ofwood bulk densities was performed. All wood specimens were cut to cubesmeasuring approximately 2.54 cm between faces and weighed. Dimensionsand acoustic velocities in each of the three principal directions weremeasured before and after carbonization. Carbonized specimens wereweighed immediately after removal from furnace. Helium density wasattempted on several carbonized species (whole specimens) but driftingof pressure readings for all but the hard maple made values unreliable.This was alleviated by grinding samples to a powder. Carbonization wasperformed in the retort furnace with a heating schedule of 15° C./hr to900° C., hold 0.5 hr, cool 50° C./hr to room temperature with a nitrogenflow rate of 0.5 L/min. Reduction in dimensions, bulk densities beforeand after, and mass yield were determined and are presented in Table 2.

The carbon yield obtained from these specimens ranged from 24.77% forbasswood to 32.48% for lignum vitae. The average carbon yield for theseven species was 28.04%. These yields are considerably higher thanthose obtained from thermal analysis experiments. This can be explainedby considering the heating rates used. The thermal analysis experimentsare performed with relatively fast heating rates compared to those usedfor the carbonization of monolithic pieces (600° C./hr vs. 15° C./hr).Slower heating rates increase the probability of cross-linking andcyclization of the decomposing polymers and reduces the volatilizationof organic molecules from the condensed phase.

TABLE 2 Data From Carbonization of Various Wood Species Lignum VitaeHard Maple Red Oak Basswood White Pine Redwood Balsa (3 each) (8 each)(7 each) (6 each) (9 each) (9 each) (7 each) mean st dev mean st devmean st dev mean st dev mean st dev mean st dev mean st dev Wood Density(g/cm³)* 1.297 NA 0.7426 0.0042 0.7043 0.0156 0.5167 0.0101 0.39870.0088 0.3656 NA 0.0111 NA Carbonized Wood Density (g/cm³)* 1.033 NA0.5861 0.0049 0.5440 0.0152 0.4035 0.0076 0.2958 0.0077 0.2707 NA 0.0673NA Axial Reduction in Length (%)** 21.67 NA 21.40 0.2564 20.69 0.167621.83 0.0516 23.48 0.2108 22.10 NA 21.80 NA Radial Reduction in Length(%)** 26.80 NA 28.90 0.5707 28.56 0.3457 33.85 0.3082 28.92 0.2774 35.30NA 23.10 NA Tangential Reduction in Length (%)** 28.83 NA 39.98 0.341237.60 0.1633 38.77 0.3266 35.44 0.4770 30.40 NA 20.10 NA Yield (%)***32.48 NA 26.48 0.0807 27.74 0.0368 24.77 0.1608 26.06 0.2088 29.720.5676 29.01 0.3614 Helium Density of Powder (g/cm³)•• NA 1.984 NA NA1.972 2.034 NA NA Data not available. Because specimen identificationwas lost, standard deviations were not available for redwood or balsa.*Bulk density of specimen in g/cm³ **Reduction in dimension of room drywood to 900° C. HTT char, in percent of original dimension ***Yieldbased on mass loss from room dry wood to 900° C. HTT char, in percent oforiginal mass ••Helium density from samples ground to powder, in g/cm³Carbonization conditions: Heat 15° C./hr to 900° C., hold 0.5 hr, cool50° C./hr to room temperature. Nitrogen flow rate 0.5 L/min, pressureslightly above atmospheric.

Reduction of dimension from carbonization in each species wasanisotropic with the exception of balsa, which was nearly isotropic. Thedata are presented in FIG. 15 as percent reduction plotted according tobulk wood density. The percent reduction in the axial direction for allspecies averaged 21.86% with a standard deviation of 0.85%.

While not intending to be bound by any particular theory, it is proposedthat the microfibrils dominate the longitudinal (axial) dimensionalchange when wood is carbonized (when no boundary restrictions areimposed). A preferred orientation of small graphitic layers may occur inthe carbonized wood. The alignment of molecules is not perfect, andthere is likely to be cross-linking and variation in the cellulosedecomposition reactions. Additional factors are likely to contribute inwood due to the many polymers which simultaneously decompose.

The dimensional changes due to carbonization in the radial andtransverse directions reflect that shrinkage is greatest in thetangential direction. Dimensional changes for all woods carbonized wasgreatest in the tangential direction except for balsa which showedessentially isotropic shrinkage. Maple, which is a diffuse-poroushardwood with numerous rays, showed the greatest tangential shrinkagefrom carbonization. Basswood, also a diffuse-porous hardwood, showedhigh transverse shrinkage and the highest radial shrinkage. The data forredwood, which has an abrupt earlywood to latewood transition and denselatewood, demonstrates less transverse shrinkage.

The various species of wood demonstrated a reduction in bulk density dueto carbonization. The results listed in Table 2 for carbonized wooddemonstrate a range in bulk density was found from 0.0673-1.033 g/cm³for balsa and lignum vitae, respectively. When the measured values forwood bulk density are plotted against those for carbonized wood, alinear relationship is observed, as shown in FIG. 16. The data in FIG.16 shows that, for the particular pyrolysis conditions, when amonolithic piece of wood is carbonized the resulting char has a bulkdensity which is about 81.76% that of the precursor. The close agreementof the data points to a linear relationship spans the entire densityrange of wood species. It is expected that other species would followthe same relationship under similar carbonization conditions. Thisallows the selection of a particular piece of wood based on the bulkdensity desired in carbonized wood.

The reduction in bulk volume of the wood species of Table 2 varied from51.2% for balsa to 68.1% for basswood. Although difficulties wereencountered when attempting to measure the helium density of themonolithic chars, a reliable value of 2.022 g/cm³ was determined for thehard maple. A value as high as this suggests that the graphitic layerplanes in the solid carbon have many defects which gives the carbonizedwood open micro-porosity. The drifting of pressure readings formonolithic specimens of other species indicates a high level oftortuosity in the capillaries of a micro-porous material. With a bulkdensity of 0.5801 g/cm³ the carbonized hard maple contains 71.3% void.

The specimens were ground to a powder and results became much morereliable for all but balsa wood char. These are listed in Table 2. Thediscrepancy between the helium density of the monolith and powder ofhard maple (0.038 g/cm³) is considered to be within experimental error.The relatively high helium densities of the powders indicates that thesolid carbons have layer planes which are open. Heat treatment withcarbon monoxide or steam may be done to open up the porosity when anactivated carbon is desired.

Acoustic velocities of the seven species of wood and carbonized wood arepresented in Table 3 along with the percent reduction in acousticvelocity. Since a liquid couplant was used for the ultrasonicmeasurements different specimens of wood and carbonized wood were used.It was found that the axial acoustic velocity in six species was reducedby the carbonization to 900° C. In lignum vitae the axial velocityincreased. In all species carbonization caused an increase of acousticvelocity in the radial and tangential directions.

TABLE 3 Acoustic Velocity Data Lignum Hard Bass- White Red- Vitae MapleRed Oak wood Pine wood Balsa longitudinal, wood* 4.27 5.54 6.01 6.115.88 5.92 5.05 longitudinal, char* 4.39 4.52 4.70 4.73 4.43 4.44 4.01longitudinal, % loss•• −2.83 18.46 21.68 22.64 24.63 25.00 20.63 radial,wood* 2.78 2.47 2.36 2.05 2.38 2.45 1.91 radial, char* 3.87 3.67 3.533.04 3.13 3.01 1.93 radial, % loss** −28.09 −48.64 −49.70 −48.44 −31.51−23.11 −0.009 tangential, wood* 2.59 1.85 1.76 1.36 1.45 2.35 1.05tangential, char* 3.57 2.67 2.28 1.82 1.80 3.06 1.29 tangential, %loss•• −37.73 44.32 −29.92 −34.32 −24.35 −30.09 −23.03 *Acousticvelocity of compressional wave, in mm/μs (1 MHz). Average of threespecimens ••Reduction in acoustic velocity, in percent of originalvalue. Average of three specimens. Carbonization conditions: Heat 15°C./hr to 900° C., hold 0.5 hr, cool 50° C./hr to room temperature.Nitrogen flow rate 0.5 L/min, pressure slightly above atmosphere.

The measured acoustic velocities demonstrated that a change in elasticanisotropy occurs with carbonization. The increased radial andtangential velocities may result from an increase in shear moduli due tocarbonization. There may also be a change in cellular anisotropy withcarbonization of aligned microfibrils in the cell secondary wall.

To study the effects of heat treatment temperature 21 specimens of tulippoplar from the same board were carbonized. Each specimen (cube) wasweighed and measured for dimension and acoustic velocity before andafter carbonization. Helium density of bulk and powdered carbonized woodwas also performed. Sets containing three random specimens were heattreated under similar conditions with each set reaching a differentultimate temperature. The temperatures for heat treatment temperature(HTT) were 400° C., 600° C., 800° C, 1000° C., 1200° C., 1500° C., and2500° C. Table 4 gives the heating schedules used for these specimens.Each specimen was first carbonized in the retort furnace where they werepacked in sawdust. For specimens heated up to 1000° C. that was the onlyfurnace used. For higher temperatures specimens were first carbonized to1000° C. in the retort furnace. The tube furnace was used to furthertreat specimens to 1200° C. and 1500° C. The graphite furnace was usedto heat specimens from 1000° C. to 2500° C. Nitrogen gas at atmosphericpressure was used in all cases.

TABLE 4 HTT Carbonization Furnace Schedule 400° C. 50° C./hr to 90° C.,hold 3 hr, 15° C./hr to 200° C., hold 0.1 hr, 8° C./hr to 400° C., hold0.1 hr, cool 100° C./hr to ambient. 600° C. 50° C./hr to 90° C., hold 3hr, 15° C./hr to 200° C., hold 0.1 hr, 8° C./hr to 400° C., hold 0.1 hr,20° C./hr to 600° C., hold 0.1 hr, cool 100° C./hr to ambient. 800° C.50° C./hr to 90° C., hold 3 hr, 15° C./hr to 200° C., hold 0.1 hr, 8°C./hr to 400° C., hold 0.1 hr, 20° C./hr to 600° C., hold 0.1 hr, 40°C./hr to 800° C., hold 0.1 hr, cool 100° C./hr to ambient. 1000° C. 50°C./hr to 90° C., hold 3 hr, 15° C./hr to 200° C., hold 0.1 hr, 8° C./hrto 400° C., hold 0.1 hr, 20° C./hr to 600° C., hold 0.1 hr, 40° C./hr to1000° C., hold 0.1 hr, cool 100° C./hr to ambient. 1200° C. As for 1000°C. specimens, then from ambient to 1200° C. at 240° C./hr, hold 10minutes, cool 240° C./hr to ambient. 1500° C. As for 1000° C. specimens,then from ambient to 1500° C. at 240° C./hr, hold 10 minutes, cool 240°C./hr to ambient. 2500° C. As for 1000° C. specimens, then from ambientto 1000° C. to 2500° C., cool at about 1000° C./hr.

All heat treatments in nitrogen atmosphere.

All carbonized specimens were crack free and uniformly reduced indimensions. That is, there was no warping or twisting from thecarbonization. Weight was measured immediately after removal fromfurnace. The data assembled from dimension and weight measurements alongwith helium densities are given in Table 5. All values are averages fromthree equally prepared specimens.

TABLE 5 Dimension and Density Values for Carbonization of Tulip Poplarat Different Temperatures loss wood mass of bulk char yield bulk bulkpowder shrink•• shrink•• shrink•• HTT ρ* bulk ρ* % ρ% He ρ* He ρ* axial% radial % tang. %  400° C. 0.5338 0.3556 31.51 9.52 1.409 1.388 10.9621.10 32.70  600° C. 0.5284 0.3620 26.97 8.80 1.500 1.524 16.14 25.8636.70  800° C. 0.5316 0.4042 25.71 6.78 1.768 1.867 19.84 29.67 40.001000° C. 0.5400 0.4203 24.85 6.44 1.778 1.971 21.16 31.59 41.26 1200° C.0.5296 0.4079 24.49 6.45 1.611 1.709 21.11 31.39 41.66 1500° C. 0.53270.4104 24.43 6.52 1.175 1.459 20.83 31.4 41.61 2500° C. 0.5127 0.395023.67 6.04 1.197 1.434 19.46 32.71 43.31

Carbon yield for all specimens is plotted as a function of HTT in FIG.17. The carbon yield obtained from carbonization diminished rapidlybetween 400° C. and 1000° C. By 1500° C. yield appeared to level off at24.40%. Yield recorded for the 2500° C. specimens was considerably lowerat 23.67%. The lower yield at 2500° C. could result from the use of thegraphite furnace. Faster heating rates could have caused mass loss inexcess of that found from heat treatments in the other furnaces.However, the lower yield is likely the result of further decompositionas a result of the extremely high temperature.

The shrinkage of tulip poplar was found to increase with carbonizationtemperature. As with other species, the reduction in dimension was leastin the axial direction, and largest in the tangential direction. Thedata for all HTT's is shown in the graph of FIG. 18. Just as yielddiminished with the highest temperatures, so does the dimension in thetangential and radial directions. However, the shrinkage in the axialdirection goes through a maximum between 1000° C. and 1200° C. There isthen an increase in axial dimension above 1200° C. while significantshrinkage occurs in the other two principal directions. This growth indimension while mass is being lost can be attributed to atomicrearrangement in the solid carbon. Density measurement results areconsistent with this theory.

The density of the carbonized tulip poplar was measured in threedifferent ways. These values can be found in Table 5. A first feature ofnote is the fact that the measured helium densities are nearly identicalfor bulk and powdered specimens carbonized to 400° C. As HTT increases,so does the difference in the measured values. It is postulated that theanatomical features retained in the bulk (monolithic) carbonized woodcauses a closing off of micropores by forming an impermeable skin.Grinding to a powder may break this skin and result in increasedmeasured density. The bulk helium density measured at both 1500° C. and2500° C. are lower than the value obtained with 400° C. specimens. Thesame phenomena did not occur in the powdered specimens, which reinforcesthe theory that the carbonized wood morphology causes a closing of themicroporosity.

Growth of graphitic layer planes of random orientation would readilycause the reduction in density found in the carbonized tulip poplar. Arandom orientation of growing layers could not lead to the bulkdimensional changes observed. A preferred orientation in the axialdirection could explain both the dimensional and helium density valuesfound as HTT increased. Layer planes aligned in the axial direction ofthe carbonized tulip poplar may account for the trends in both densityand dimension by giving axial growth and closed micropores at the highertemperatures studied. Since mass is lost, and interlayer spacingdecreases, some radial and tangential dimension reduction would beexpected. In addition, the theory of microfibril dominance for axialshrinkage establishes some degree of preferred orientation of layerplanes in the longitudinal principal direction of carbonized wood.

In FIG. 19, measured quantities for carbonized tulip poplar bulkdensity, helium density of bulk and helium density of powder, arenormalized to their 400° C. value. All densities were found to increaseup to 1000° C. At higher temperatures the helium densities dropped toless than, or close to, their value at 400° C. while the bulk densitydropped off only slightly. This indicates that the mechanisms involvedin restructuring the carbonized wood above 1000° C. affect themorphology of the microstructure much more than the morphology of themacrostructure.

The sets of carbonized tulip poplar were also measured for acousticvelocity in the three principal directions. The average values obtainedare listed in Table 6 along with the velocities of the specimens beforecarbonization.

TABLE 6 Acoustic Velocities for Range of Carbonization Temperatures woodwood wood char char char delta delta delta HTT axial* radial* tang*axial* radial* tang* axial•• radial•• tang••*  400° C. 5.90 2.18 1.532.17 1.62 0.75 172 25.8 51.2  600° C. 5.90 2.17 1.51 2.97 2.18 1.11 98.9−0.276 26.4  800° C. 5.88 2.17 1.49 4.05 2.87 1.22 45.1 −32.4 18.1 1000°C. 5.87 2.17 1.53 4.73 3.33 1.53 24.0 −53.5 0.196 1200° C. 5.86 2.181.51 4.95 3.46 1.63 18.5 −58.7 −7.91 1500° C. 5.88 2.16 1.52 4.95 3.381.73 18.8 −56.3 −13.8 2500° C. 5.77 2.18 1.44 4.92 2.98 1.48 17.3 −36.7−3.06 *Acoustic velocity of compressional wave, in mm/μs (1 MHz).Average of three specimens. ••Reduction in acoustic velocity, in percentof original value. Average of three specimens.

All three directions exhibit increasing velocity from the 400° C. value,with increasing carbonization temperatures up to 1200° C. Velocity inthe axial direction levels off at approximately 5 mm/μs, a reduction of15% from the value for wood. Velocities in the tangential and radialdirections surpassed the counterpart velocities measured beforecarbonization by up to 58.7% radially (delta radial and delta tangentialin Table 6). These velocities then diminished slightly at highertemperatures, the radial starting at 1200° C. and tangential at 1500° C.

The trends in acoustic velocity with HTT serve to support the mechanismof atomic ordering within the carbonized wood. Acoustic velocity wasfound to increase above 1000° C. where the powder density measurementbegins to decline. A lateral growth of layer planes would account forthis divergence in the two parameters. Lateral growth associated withatomic ordering will increase material stiffness if a preferredorientation of layers is present. Increased stiffness is indicated bythe increased velocities up to about 1200° C. The decrease in radial andtangential velocities at the highest temperatures may result from growthin layer height within the solid carbon. This is plausible since thereduction in dimensions that occur would suggest shrinking celldiameters which should cause an increase in velocity owing to a shorterpath-length which a stress wave traverses. An increase in layer height,with surface normals parallel to the propagation direction, will cause areduced velocity. Thus, preferred orientation of growing graphiticlayers leads to changing physical properties and dimensions in thecarbonized wood.

Samples of the carbonized poplar were prepared for x-ray powderdiffraction analysis by grinding in a mortar and pestle. Powder wasplaced on a sample holder using vacuum grease as a glue. Samples heattreated at 2500° C. down to 400° C. were scanned using identicalprocedures. FIG. 20 is in an overlay of the results from each specimenshowing intensity of diffracted beam versus Bragg angle. Diffraction forthe {002} (26° 2-Theta) planes and the overlapping {101},{100} (43°2-Theta) planes clearly changes with increasing HTT. The narrowing ofpeaks is indicative of developing atomic order in the carbonized wood.Significant increase in the {002} reflection between 1500-2500° C.demonstrates that increased layer height and order occurred. Thediscontinuity in the peak may result from catalytic graphitization byinorganics within the precursor wood. Continued lateral growth of layerplanes is indicated by the increasing intensity of the doublet at 43°2-Theta.

Two samples of carbonized wood were investigated for mechanicalproperties. Uniaxial compression parallel to the carbonized wood axialdirection was performed by end loading the specimens. Strain wasmeasured with a 1 inch gauge length extensometer placed on specimenaxial-radial face. Stress was determined by dividing load cell readingby specimen cross-sectional area. A load rate of 10 kip/min was used tobring specimens to failure.

Two specimens were carbonized for the mechanical testing, one tulippoplar and one southern yellow pine pressure treated with a conventionalcopper-chrome arsenate (CCA) formulation. Both were carbonized in theretort furnace to 600° C. and then to 1550° C. in the tube furnace. Oncecarbonized, they were ground to precise dimensions on a milling machinewith a ceramic abrasive wheel. This was followed by a light sanding with600 grit paper. Specimen dimensions were approximately 1″ radial×1″tangential×2.75″ axial. The tulip poplar contained approximately 11growth rings, and had a bulk density of 0.398 g/cm³. The yellow pineabout 8 rings, bulk density of 0.376 g/cm³.

First a specimen of tulip poplar wood was prepared and tested in themanner described above. The specimen failed in the classical shearkink-band common to wood. The carbonized specimens were tested next. Theresults for all three are plotted in FIG. 21, modified by converting themeasured values for stress and strain to positive values (conventionalcompression values are negative). The poplar wood displayed greaterstiffness than the carbonized poplar but, surprisingly, less strength.The response of the wood was at first linear, then non-linear above 6000psi stress. The kink-band mode of failure is indicated by a “dip” in thecurve just prior to catastrophic failure. The response of the carbonizedspecimens was linear, then displayed graceful brittle failure.Specifically, there was some audible acoustic emission and noticeablelongitudinal splitting of the specimens before complete catastrophicfailure. Stiffness measured as the slope of the linear region was 2.06Msi for poplar, 1.30 Msi for carbonized poplar and 1.23 Msi for thecarbonized treated yellow pine. Ultimate strengths measured 8.6 ksi,11.6 ksi and 8.2 ksi, respectively. Assuming no variation in the tulippoplar, the stiffness was reduced due to the carbonization by 37% andstrength increased by 35%.

Thus, in accordance with the present invention, monolithic samples ofcarbonized wood can be produced by appropriate selection of time,temperature and atmospheric parameters. In particular, heating ratesneed to be slow enough to avoid the formation of cracks which aretypically associated with the carbonization of wood. Heating ratesproper for one wood species may not be appropriate for another. Thecritical temperature range, based on maximum decomposition rates, isfrom approximately 200° C. to 400° C., but care need also be takenoutside of this range. Wood which has a high moisture content ispreferably dried at temperatures below 100° C. to prevent steampressurization and non-uniform shrinkage, both of which may lead tocrack formation.

Crack-free specimens may be produced even when the wood containsintergrown knots. The anatomical features of the precursor wood wereretained using the present method. The resultant carbonized wood hassufficient mechanical strength to be machined to exact dimensions usingconventional tools.

The carbonization parameters of the present invention may be modified.For example, the use of increased pressure may substantially increasesolid carbon yields. Modification of carbonization atmosphere could bestudied with the intent of producing different decomposition mechanismsand, possibly, improvements in yields and properties. Chemical additivesto precursor wood may give similar results.

Carbonized wood produced in accordance with the present invention may beused in applications where synthetic carbon foams are currently beingemployed. The morphological characteristics of the carbonized wood offerdistinct advantages in some applications. For instance, the highlyaligned and elongated longitudinal cells are ideally suited for gastransport in the axial direction of carbonized wood. A rough measure ofthe permeability of some specimens of carbonized wood was made by use ofa small plastic funnel attached to a hose from a vacuum pump.Measurements of the pressure drop across a sample indicated some hadhigh axial permeability compared to others. Permeability in radial andtangential directions was much lower. This approach aided in theselection of a carbonized wood with suitable permeability forinfiltration by polymers. It also demonstrated that the anisotropicpermeability of the precursor wood is maintained, a feature whichdistinguishes carbonized wood from carbon foams. The aligned cells inthe carbonized wood also allows for higher stiffness than that found incarbon foams. This is certainly an advantage when structuralapplications are considered.

In accordance with an embodiment of the present invention, the adverseimpact on the environment by pressure treated lumber may be remediatedby recycling of these chemically treated forest products. Carefulcarbonization of pieces of CCA treated wood retains some, or all, of thecopper, chrome and arsenic compounds in a highly porous solid carbon. Atthat stage the inorganics can be leached out and reclaimed. Theremaining porous carbon can be sold for ore reduction, metallurgicalprocessing or any other suitable industrial use. As an alternative,products such as monolithic ceramics and composites can be produceddirectly from the porous carbon derived from pressure treated lumber.

Several examples were performed to attempt to determine whether CCAtreated wood could be carbonized in a manner similar to untreated wood,and whether the addition of the inorganics influences the decomposition.A sample of 2% CCA solution was obtained from Hickson Corporation(Conley GA) which contained 0.95% CrO₃, 0.37% CuO and 0.68% As₂O₅(percent on oxide basis). Some of the solution was left in an openfurnace at about 100° C. for several hours to evaporate off the water.This produced a gummy residue of concentrated CCA which readily absorbedmoisture from the air when left in an open room.

The resulting viscous liquid was placed in an alumina sample cup forthermal analysis (TGA). This was performed in an argon atmosphere and afurnace schedule of 10° C./min to 90° C., hold 10 min, 10° C./min to1000° C., cool at 20° C./min. Weight loss was found through the entirehold period and increased as temperature raised above 90° C. At 200° C.approximately 28% weight loss had occurred which was attributed to waterloss. Between 200° C. and 800° C. an additional 10% of the originalmaterial was lost, mostly in two steps at 340° C. and 500° C. Above 800°C. a rapid reduction in weight to 38% was observed. The data shows thatthe CCA concentrate decomposes at certain temperatures, ultimatelyloosing 62% of its weight.

Thermal analysis was used for studying the carbonization of CCA pressuretreated wood. Commercially available CCA treated yellow pine wasprepared in the same manner as the other wood specimens. Several sampleruns were performed and each gave similar results. The results indicatedthat decomposition of CCA treated wood proceeds through the same stagesas untreated wood. None of the decompositions found in the CCAconcentrate appeared in the data for the treated wood. Considering thesmall quantity of CCA (0.4 lb/ft³) it is possible that any alterationsin wood decomposition mechanisms, or the presence of CCA decomposition,are undetectable by this method.

Elemental analysis by Energy Dispersive X-ray (EDX) technique of theScanning Electron Microscope (SEM) was performed to determine whetherany of the copper, chrome or arsenic remained in the carbonized pressuretreated wood. The first approach taken was to coat a piece of untreatedchar with the CCA concentrate to establish the capability of detectingthe elements in a best case scenario. This coated sample was examined atlow magnification by EDX. The elements chromium, copper and arsenic wereclearly detected.

Further elemental analysis was performed on commercially available CCAtreated yellow pine and the same carbonized to 600° C., 800° C. and 900°C. In all cases positive identification of chromium, copper and arsenicwas made. The data shows the retention of Cr, Cu and As, as well as thepresence of sulfur, potassium and calcium. The results from theelemental analysis by EDX clearly indicate that the carbonization of CCAtreated wood produces a porous solid carbon with some of the hazardouselements retained.

Attempts to characterize crystalline phases as a function of HTT indifferent samples of carbonized wood resulted in the discovery ofcatalyzed graphitization in CCA treated yellow pine. X-ray diffractionanalysis of untreated carbonized wood indicated a low degree of atomicorder in specimens heat treated to 1500° C. Broad peaks from {002}reflections indicated non-graphitic carbons. Reflections from the {100}and {101} planes were broad and overlapped.

Two precursors were selected for the heat treatment study, commerciallyavailable CCA treated yellow pine and Honduran mahogany as an untreatedreference. Samples of both were carbonized at rates slow enough to avoidcracking (50° C./hr) then heat treated to either 900° C., 1100° C.,1300° C., 1400° C. or 1500° C. in an argon atmosphere. X-ray diffractionwas then used to detect the onset of catalyzed graphitization. None ofthe prepared samples showed indications of three-dimensional long rangeorder for graphite at 1400° C. or below. At 1500° C. the CCA treatedsample gave a strong peak from the {002} reflection. This is shown inFIG. 22 where diffraction data from treated samples heat treated to1400° C. and 1500° C. are plotted on the same graph. Catalyzedgraphitization of the carbonized treated wood was found to occur between1400° C. and 1500° C. HTT.

The presence of a graphitic phase in the carbonized treated woodsuggested the possibility of being able to alter the mechanicalproperties of monolithic carbonized wood via micro-structuralmodification. One specimen of CCA treated yellow pine heat treated to1550° C. was tested to failure in compression. These results are in FIG.21. The measured stiffness from the test was 1.23 Msi, the same order ofmagnitude as poplar wood and carbonized poplar. Also, ultrasonicvelocity measurements indicated no significant increase from catalyzedgraphitization.

The use of the Honduran mahogany as a reference in the catalyzedgraphitization experiment gave unexpected results. The wood, whencarbonized to 1500° C., gave no indication for graphitic carbon by x-raydiffraction analysis. However, at HTF's of 1100° C., 1300° C., and 1400°C. the presence of calcium oxide (CaO, lime) was found. This presumablyformed from thermal decomposition of calcium oxalate (CaC₂O₄) to calciumoxide. The tropical hardwoods are known for containing high levels ofinorganics, especially silica and crystals of calcium oxalate.

In accordance with an embodiment of the present invention,carbon/polymer composites are fabricated from carbonized wood. Theporous carbon monoliths produced by carbonization of naturally fibrousplants offer a unique framework from which a composite can be produced.Since anatomical features are retained during carbonization, a porousmonolith can be infiltrated with gases or liquids creating a multi-phasematerial with properties different from its constituents. The anisotropyinherent in the precursor is at least partially retained duringcarbonization. Properties can also be tailored, as in CRP's, by stackinglayers to make a laminate. The selection of precursor wood can be usedto determine many of the properties of the final carbon reinforcedcomposite. In particular, carbonized wood density can be selected basedon initial wood density. Carbon reinforced polymer composites using woodmonoliths as precursors may thus be formed.

To demonstrate the carbon/polymer composite embodiment, a polymer withlow viscosity which readily wets carbon was selected for impregnation.The capability to work at room temperatures with minimum equipment wasalso preferred. An amine cured epoxy was selected which had sufficientworking time to allow for thorough infiltration before hardening.Pro-set® 125 resin and 229 hardener produced by Gougeon Brothers Inc.met the processing criteria.

To be assured that the carbonized wood was permeable, specimens weretested for pressure drop as described previously. Tulip poplar, tupeloand yellow pine were found to have relatively low axial pressure drop,and therefore reasonable permeability. It was also determined that thecarbonized sapwood was much more permeable than that from heartwood.Tulip poplar is a diffuse porous wood and is more likely to give uniforminfiltration. Yellow pine has relatively good mechanical properties andhigh permeability, making it a preferred polymer composite precursor.

To take advantage of the natural directional permeability retained incarbonized wood a method for resin transfer which used a vacuum assistwas used. A schematic and illustration of the setup is shown in FIG. 23.A vacuum is applied to one end of a specimen to draw resin through fromthe other end. Many of the polymeric materials used in the vacuumassisted resin transfer setup were manufactured for producingconventional composites. A carbonized specimen was first wrapped in aporous release cloth. Next, small pillows of bleeder cloth werepositioned at each end of the specimen to evenly distribute the resinflow. Tubing placed onto the bleeder cloth at one end passed to a vacuumpump by way of a fluid overflow flask. Tubing on the other end of thespecimen acted as a resin supply line by connecting to a squeeze bottlefilled with mixed epoxy. The flexible tubing used could be folded overto stop resin flow while a valve in the low pressure side enabled therelease of the vacuum. The sample, cloths, and tubing ends were thenenclosed in a sealed vacuum bag using conventional bagging film andsealant. Adequate seal was assured by a pressure gauge attached to thevacuum tubing.

Specimens with dimensions of several centimeters were infiltrated usingthe vacuum assisted resin transfer setup. A specimen was wrapped andplaced into a vacuum bag as described. Drawing a vacuum caused thebagging film to shrink up tightly against the carbonized wood. No damageto specimens was noticed due to the atmospheric pressure. Resin andhardener were mixed in the squeeze bottle which was then attached to thecrimped (flow shut off) material feed tube. Resin was gradually allowedto pass into the bag by uncrimping the tube for short periods. Resinflow was relatively slow. The vacuum was periodically interrupted toreduce the rate of resin boiling which occurred at the lowest pressures.Resin transfer was continued for several minutes after it began flowinginto the vacuum tube. The release paper was continually observed forresin wetting, a sign that resin was flowing through the carbonizedwood. When transfer was believed complete the vacuum and material tubeswere closed off. Infiltration took approximately 25 minutes forspecimens measuring approximately 3×3×8 cm. The epoxy was usuallyallowed to cure before the composite was removed from the bag.

Elevated temperatures from the epoxy cure were measured. A thermocouplewas placed on the surface of a carbonized wood specimen which measuredapproximately 3×3×8 cm. After epoxy infiltration the measuredtemperature eventually reached 72° C. Internal temperatures wereprobably higher.

The first specimen infiltrated was carbonized CCA treated yellow pinemeasuring 4×3×8 cm (HTT 600° C.). Radiography of the resulting compositeindicated infiltration of the porous carbonized wood was uniform.

The next carbon-epoxy composites produced were from two specimens of CCAtreated yellow poplar. One had been carbonized to 600° C. The otherspecimen had been heat treated to 1550° C. which produced a graphiticcarbon. Each specimen measured approximately 2×4×5 cm. Infiltration wasperformed in separate bags. The composites produced were uniformlyinfiltrated as determined by radiography. These radiographs are shown inFIG. 24. The composite from the 600° C. specimen had a limited amount ofearlywood cracking. The 1550° C. specimen had no cracks, perhaps due toincreased stiffness and strength from the higher HTF. Also, thedimensional reduction was greater in the 1550° C. specimen so that theearlywood regions were slightly narrower and less prone to crackformation.

The carbon-epoxy composites were machined to precise dimensions on amilling machine using an abrasive wheel. The composites were thenpolished with increasingly finer abrasives (to 0.05 μm). The resultingcarbon-epoxy composites exhibited all of the visual features found inthe precursor wood grain. A photograph of the 600° C. composite is shownin FIG. 25.

Other carbonized wood species were successfully infiltrated with epoxyto form composites. Both tulip poplar and tupelo were successfully usedas precursors. Other species can also be used, provided that theypossess adequate permeability after carbonization.

Optical microscopy of polished surfaces was used to assess the qualityof the composites produced. Some specimens were cut in half to inspecttheir interior, others were inspected close to the original compositesurface. FIG. 26 shows the abrupt earlywood-latewood transition in acomposite produced from graphitized CCA treated yellow pine (HTT 1550°C.) in the RT plane at a magnification of 50×. The same specimen isshown in the micrograph of FIG. 27 in the LR plane at a magnification of50×. The majority of the section is uniformly infiltrated. Additionalmicrographs of the specimen are presented in FIGS. 28 and 29. FIG. 28 isfrom the LT plane of the graphite-epoxy composite, showing the earlywoodregion at a magnification of 400×. FIG. 29 is also from the LT plane ofthe composite, showing the latewood region at a magnification of 200×.These micrographs show the anatomical features retained from theoriginal wood.

Composites prepared from CCA treated yellow pine carbonized to 600° C.were inspected after polishing. FIGS. 30 and 31 are micrographs showingdifferent magnifications of a section revealing the RT plane. FIG. 30shows the earlywood-latewood transition at a magnification of 125×,while FIG. 31 shows the latewood region at a magnification of 500×. Fewvoids were found in the areas examined. The graphite-epoxy compositedescribed above had a bulk density of 1.16 g/cm³. Using a helium densityof 1.20 g/cm³, a bulk density of 0.381 g/cm³ for the graphitized yellowpine, and a density of 1.14 for the epoxy, the porosity contained in theepoxy phase accounted for less than 1% of the total composite volume.

The vacuum assisted resin transfer method was useful for achievinguniform infiltration of epoxy in the carbonized wood specimens.Improvements can be made to speed up the process and to enable largerpieces to be produced. Placing the bagged specimen and materialreservoir into a vessel capable of applying an over-pressure wouldenable a higher pressure gradient to be achieved. An additional benefitwould be that resin boiling could be avoided. Bagging the carbonizedwood was done to promote directional flow of resin along the grain. Thismay be unnecessary and a chamber capable of pulling a vacuum andapplying pressure may be all that is needed.

Mechanical testing was performed on one specimen of carbon-epoxycomposite derived from poplar (HTT 1550° C.). The composite was preparedby vacuum assisted resin transfer as described above. An epoxy specimenwas also prepared for mechanical testing. Both specimens measuredapproximately 2.5×2.5×7 cm. The results from these mechanical tests areshown in FIG. 32 along with those from the testing of poplar andcarbonized poplar.

The mechanical tests reveal excellent results. Table 7 gives a summaryof the measured values.

TABLE 7 Mechanical Properties of Carbon-Epoxy Composite Derived fromPoplar Carbonized poplar bulk density ρ_(BC) = 0.4104 g/cm³ Carbonizedpoplar monolithic helium density ρ_(CHe) = 1.175 g/cm³ Epoxy densityρ_(E) = 1.143m g/cm³ Carbon-epoxy composite density ρ_(CE) = 0.9294g/cm³ Stiffness of bulk carbonized poplar E_(BC) = 1.380 Msi Stiffnessof epoxy E_(E) = 0.500 Msi Stiffness of carbon-epoxy composite E_(CE) =1.550 Msi

These values may be used to analyze the appropriateness of using a ruleof mixtures for assessing the stiffness of the composite. The rule ofmixtures used here for stiffness is based upon each phase beingconsidered as a spring in parallel to the next phase. This implies thateach phase is continuous and of uniform cross-section throughout theheight of the load bearing section.

The density of the composite was 0.9294 g/cm³ which is less thanpredicted from a rule of mixtures analysis. Using a helium density formonolithic carbonized poplar of 1.175 g/cm³ and a bulk density of 0.4104g/cm³, a volume fraction for the carbon phase is 0.3493. That leaves avolume fraction of 0.6507 for epoxy to fill. These volume fractions andthe density values in Table 7 give a predicted density for the compositeof 1.154 g/cm³. This indicates a void percentage of 19.65% in thecomposite (actually, this is the porosity contained in the epoxy).

The measured stiffness of the carbon-epoxy and the carbonized poplarwere less than the precursor wood. The carbonized wood bulk densitydivided by the helium density gives the fraction of carbon acting asload support under idealized conditions, V_(C)=0.3493. This indicatesthe stiffness of the carbonized wood phase was:

E _(BC) /V _(C) =E _(C)=3.951 Msi,

giving a rule of mixtures for the composite with no void content of

V _(C) E _(C) +V _(E) E _(E) =E _(CE)=1.705 Msi.

This gives a higher value than that measured for the composite, 1.550Msi. If the void volume fraction of 0.1965 (V_(V)) is included in therule of mixtures,

V _(C) E _(C)+(1−V _(C) −V _(V))E _(E) =E _(CE)=1.607 Msi,

a closer value is obtained. This does not consider the distribution ofthe void content or the closed porosity within the solid carbon. Alsounaccounted for is the volume fraction of ray cells. It does suggestthat a rule of mixtures may be appropriate for the composite when loadedparallel to the longitudinal cells of the carbonized wood.

The strength of the composite was 22.4 ksi. This is 200% higher than thecarbonized poplar and 250% higher than the poplar. The higher strengthof the composite may be attributed to the epoxy providing lateralsupport of the thin walled carbon cells resulting in decreased tendencyfor Euler buckling. Failure was preceded by an audible acoustic emissionfrom splintering of the specimen edge. Failure occurred in a brittlemanner. The composite exhibited mode I fracture by tensile failureperpendicular to the LR plane. This type of compression failure issimilar to that found in cross-ply composite laminates. The poplarderived carbon-epoxy composite demonstrates that ray cells act aslateral reinforcement to the longitudinal cells. Failure occurred in theunreinforced transverse direction (tangential) and appeared very similarto delamination in cross-ply composite laminates.

The composite specimen was not fully impregnated with resin. Theradiograph indicated significant porosity which was verified by densitymeasurement and inspection of the specimen interior after failure. Lessporosity would probably improve composite mechanical properties.

Increased stiffness of the carbon phase could substantially improvecomposite strength. The composite tested exhibited a relatively highstrain to failure, approximately 1.5%. Strain to failure is typicallyused as a design criteria when composites are produced. For example,high modulus PAN carbon fibers show less than 1.5% strain to failurewhen tensile loads are applied. Increasing the stiffness of thecarbonized poplar would significantly increase composite strength if asimilar strain to failure was achieved.

Increasing the stiffness of the carbonized wood may be accomplished byproducing a higher degree of preferred orientation of the graphiticdomains within the solid carbon. This could possibly be accomplished bystretching of the monolith at some latter stage of carbonization.Alternatively, the carbonized wood could be infiltrated with a polymersuch as PAN which could then be carbonized.

The carbon-epoxy composites described above were produced fromrelatively thick samples of carbonized wood. Some thinner specimens wereproduced which were laminated to form a carbon-epoxy compositeresembling plywood. An example is shown in FIGS. 33 and 34. Thelaminated composite was made by gluing together three pieces ofcarbonized poplar with epoxy. Once cured, the laminate was immersed inuncured epoxy and placed in a vacuum desiccator. A series of vacuum holdand release cycles was capable of forcing the epoxy into the permeablecarbonized poplar. After the epoxy matrix cured, the sample was machinedand polished. The photograph of FIG. 33 shows an edge view of thecross-ply composite (0, 90, 0). FIG. 34 gives a top view of the samespecimen which reveals multiple ray flecks.

The carbon-epoxy laminate appeared fully impregnated with epoxy. Thefact that this was accomplished by atmospheric pressure may beattributed to the relatively small size and high permeability of thecarbonized poplar. The initial impregnation experiments describedpreviously were successfully performed on less permeable species. Theresults from the composite laminate indicates that inducing adirectional flow may not be needed for resin impregnation in all cases.

These results also demonstrate the potential for producing complexcomposite structures with sections cut and joined by techniques similarto those used in woodworking. It should be possible to use complexjoinery for building structures with easily worked carbonized wood. Oncejoined and held together by adhesives such as epoxy, full impregnationcould be performed in a suitable pressure vessel. Pieces may also beimpregnated with epoxy before joining. Both the carbonized wood and theresulting composites are easily machined with standard tools.

Other resin impregnation experiments were performed on different woodspecies and on bamboo. Other features of this embodiment include thepossibility of using wood chips, sawdust, weaves of rattan or cotton orwood strips, and many other naturally fibrous plants.

One of the unique features of producing composites by infiltration ofcarbonized wood is that net shape processing is easily achieved. Thecarbonized wood can readily be machined to close tolerances beforeimpregnation. The infiltration of the polymer can be accomplishedwithout disturbing the geometry of the carbon structure. Also, moldingis not necessary.

In accordance with another embodiment of the present invention,carbonized wood is used as a precursor for carbon-carbon composites. Asimilar process to that described above for the production ofcarbon-polymer composites using phenolic resins as the impregnate wasconducted. Two carbonized wood specimens were selected for impregnation,one poplar (HTT 600° C.) and one CCA treated yellow pine (HTT 1500° C.).Both specimens measured approximately 2.5×3 cm in cross section. Thepine was 4 cm long, while the poplar was 6 cm long. Each specimen wasplaced in a vacuum bag for resin transfer as described previously.Phenolic resin in an organic solvent (SC-1008 from Durite Inc.) was usedfor infiltrating each specimen. Due to the viscosity of the phenolic, itwas warmed with hot water prior to impregnation. Vacuum assisted resintransfer was successful and the bagged specimens were placed in a warmedfurnace to set the phenolic at 190° C.

Some of the phenolic which had impregnated the carbonized wood specimensflowed out while curing in the closed bags. The outgassing of vaporscaused the bags to inflate so that the phenolic was not fully contained.The specimens were then carbonized in the retort furnace using a heatingschedule of 50° C./hr to 700° C., cool 150° C./hr. The resultingspecimens had a covering of glassy carbon bubbles which was readilysanded off. An increase in bulk density indicated porous carbon-carboncomposites had been made.

The porous carbon-carbon specimens were then reimpregnated using adifferent method. The viscosity of phenolic resin was reduced byaddition of propanol to improve flow. The specimens were then placed ina beaker filled with warmed phenolic and kept immersed by weights. Thebeaker was then put into a vacuum desiccator for a series of lowpressure cycles. Specimens were then removed and placed in a warmedfurnace for phenolic cure. The impregnation cycle was repeated andspecimens allowed to cure. A second carbonization was then performedproducing specimens with surfaces covered by glassy carbon bubbles whichwere sanded off.

The carbon-carbon composites were still relatively high in porosity.Bulk density measured 0.572 g/cm³ and 0.576 g/cm³ for the pine andpoplar, respectively. This amounted to a 51% and 59% increase over theircarbonized wood state. A third impregnation/carbonization sequence gaveno increase in bulk density indicating the carbon-carbon compositescontained considerable closed porosity. Radiography showed that thespecimens had a uniformly distributed matrix. The specimens are shown inFIG. 35.

Alternative methods for polymer impregnation and carbonization ofcarbonized wood are possible. The use of a vessel capable of applyingboth vacuum and overpressure may improve impregnation. Carbonization ofthe matrix phase may give a higher yield if slower heating rates areused and a method for preventing outflow of the uncured phenolic isutilized. This could be accomplished by curing bagged specimens whileexternal pressure is applied. Alternative precursor polymers for matrixcarbon can be used in order to appropriately match the carbonized woodphase.

The carbon-carbon composites of the present invention may be used forvarious applications. For example, brake shoes and other hightemperature applications are suitable. Testing of prototype productssuch as brake shoes or ablative shields may readily be performed in alaboratory scale apparatus. Wear testing of disc brake shoes could beperformed on conventional disc rotors mounted on a machinists lathe orelectrically driven automobile axle. Ablation studies may be performedin a high temperature furnace using high temperature gas streamsprovided by gas tanks. The utilization of ablation resistant coatingssuch as silicon carbide is also possible.

In accordance with a further embodiment of the invention, carbides canbe produced using carbonized wood as a precursor. Not only can thisprovide for improved mechanical properties in a particular orientation,it can also allow for increased fluid flow along a specific direction.This allows for improved infiltration of reacting fluids and vapors. Thedirectional permeability can even be retained in a porous ceramic givingit flow characteristics unattainable in reticulated carbon foams.

Three processes can be used to convert porous carbonized wood materialsto ceramic. These are infiltration with molten precursor, infiltrationwith colloidal suspension of nano-sized particles and vaporinfiltration. Examples of the three routes to conversion are:

(1) Liquid infiltration/reaction process,

Si+C→Sic;

(2) Sol-Gel infiltration/reaction process,

SiO₂+3C→SiC+2CO or,

2SiO₂+3C→SiC+SiO+2CO

SiO+2C→SiC+CO;

(3) Chemical vapor infiltration/reaction process,

SiH₄+C→SiC+2H₂.

Different approaches to making silicon carbide from carbonized wood wereused. One entailed the infiltration of wood with a sol-gel of silica.The second used carbonized wood infiltrated with silica sol-gel. Thethird used liquid silicon infiltration and reaction to make siliconcarbide.

Pine, red oak and mahogany wood samples were soaked in a sol-gel (Nyacol2040 silica sol by PQ Corp.) along with carbonized pine and poplar.These were immersed in liquid and placed under a vacuum, then leftovernight under atmospheric pressure. Samples were then dried in afurnace at 100° C. for two hours. Once dry, they were placed on a flatgraphite boat with a specimen of carbonized poplar and carbonized redoak, both having a small (approximately 0.5 g) fragment ofsemi-conductor silicon placed on top (axial direction up). The boat andsample were placed in a tube furnace with an argon flow of 1 L/min.Temperature was manually raised to 1520° C. and then cooled manually.Total time above 1400° C. was approximately 30 minutes.

All specimens appeared to have some regions of conversion by exhibitingcolors ranging from light gray to green. The specimens soaked in silicasol were uniform in color, those with silicon fragments placed on themwere greenish in some areas and still black in others. The samples werescanned whole by x-ray diffraction (XRD) for crystal phase analysis. Allsamples were found to contain some SiC. The results from XRD of themahogany wood/silica sol precursor is given in FIG. 36. The diffractionpattern contained two sharp peaks matching those for beta SiC (zincblend structure). Diffuse diffraction at 26° and 43° 2-theta indicatenon-graphitic carbon still remains. The specimen had a faint green colormixed with black.

The pre-carbonized specimens mixed with silica sol also gave anindication of SiC. In the carbonized oak/silica sol specimen a peak at22° 2-theta indicated there was also some residual silica, detected ascristobalite. The specimen was scanned whole, once with the grain (axialdirection) parallel to the scanned diffraction plane and onceperpendicular. These are shown in the overlay of FIG. 37. Thecristobalite peak disappears when the orientation is altered, suggestinga preferred orientation of the crystal silicate phase. There is alsosome change in the broad diffuse peaks for non-graphitic carbon,indicating a preferred orientation of that phase also.

The best results were obtained from the carbonized specimens withsilicon placed on them. These had regions which were distinctlydifferent due to the conversion to carbide. The converted regions werevery hard and had a light green tint. Pores observable withoutmagnification in the oak appeared to still be open. XRD results from thepoplar specimen are presented in FIG. 38. Intense narrow peaks areindicative of highly crystalline SiC. X-ray radiography confirmed visualobservations of non-uniform mixing of silicon in the porous carbons.Scanning electron microscopy revealed carbide crystallites and indicatedthe transition zone between carbide converted regions and theunconverted solid carbon.

In another process, specimens of carbonized wood (HTT 600° C., red oak,balsa and basswood) were cut to approximately 5×4×3 cm, the shortestdimension being in the longitudinal direction. The specimens were thenmachined on one end (RT plane) to form a shallow (about 3 mm) trough inwhich silicon was placed. Lump silicon (Aldrich Chem. Co. #26, 742-2,98.5% pure) was added to each trough in a stoichiometric amount for eachspecimen to be completely converted to SiC. The specimens were placed ona flat graphite boat in a tube furnace under an argon flow rate of 0.2L/min. The furnace was programmed for a ramp rate of 240° C./hr to 1500°C., hold 20 min, cool at 240° C./min.

All three specimens showed signs of partial conversion to carbide. Theregions which had converted were very hard and had a greenish metallicluster. Radiography confirmed that the carbonized wood had not beencompletely converted. It was apparent that the liquid silicon had passedthrough the porous carbonized wood converting regions where it hadmixed. It did not readily flow outward and thus the sides of thespecimens were unconverted. A piece of carbonized manila paper placedbetween the samples and graphite boat had signs of conversion to carbideand excess Si, also verifying that liquid Si had passed through thespecimens. XRD of the specimens ground to a coarse powder identifiedbeta-SiC and excess Si. SEM analysis of the specimens confirmed partialconversion to SiC.

In order to get complete mixing of Si in the carbonized wood monoliths,a recess in a graphite furnace boat was made for holding molten silicon.Specimens could be immersed, end grain down, in a shallow pool of liquidwhich could be drawn up by capillary forces. Carbonized wood blocks (oneinch cubes before carbonization) were placed on a bed of lump siliconlaying on the bottom of the furnace boat. Small pieces of silicon wereplaced on top of each to weigh down the light specimens. Six differentspecies of carbonized wood (maple, red oak, basswood, white pine, balsaand redwood, HTT 900° C.) and a carbonized piece of bamboo wereconverted using greater than a stoichiometric quantity of silicon. Thesewere heated in an argon atmosphere (0.02 L/min) with a furnace scheduleof 240° C./hr to 1500° C., hold 10 min, cool 240° C./min.

The specimens appeared fully converted. Samples ranged in color from ablack-green to light gray where some surface slag appeared. Thespecimens readily scratched metals and glass, and still retained allvisible anatomical features of the precursor wood. Dimensions weremeasured before and after conversion and only minor (±3/1000 per inch)differences were found. Near-net shape specimens of SiC were thereforeproduced.

Some surfaces of the specimens had lustrous regions or droplets (lowwetting angle) of residual Si. XRD of whole specimens identifiedbeta-SiC and residual Si. Some scans gave stronger indication of Si thanothers. FIG. 39 shows the result from XRD of red oak converted to SiC.Considerable Si was detected on the surface scanned. The pine specimenwas crushed in a press and fragments examined in the SEM. Most of theoriginal cell lumens were completely filled with residual Si. The cellwalls were a different shade in the images indicating they had beenfully converted to SiC. The Si in each lumen contained fracture surfacesof slightly different orientation suggesting each had a slightlydifferent crystallographic orientation. The bamboo specimen wassectioned in a water cooled diamond saw revealing the anatomicalfeatures retained within it. The largest pores of the precursor bamboowere left unfilled by the residual Si, while most of the fibers werefilled as seen in the micrograph. The bamboo retained its tubular shapewithout signs of distortion.

In another example, two board shaped specimens of carbonized redwood(HTT 900° C.) with dimensions of about 0.8×2.6×7 cm (long in axialdirection) were packed in the graphite boat such that the grain layhorizontally. Silicon was placed underneath and on top, with themajority being piled near the endgrain with the intent of having theliquid Si wick horizontally into the porous carbon. More than twice theamount needed for full conversion was added, 50 gm of Si for 9.5 gmsolid carbon (22 gm is stoichiometric amount). The specimens were heatedin an argon atmosphere at 240° C./hr to 1500° C., hold 2 hr, cool 240°C./hr. The two redwood specimens appeared fully converted when observedvisually. Each had gained more mass than needed for full conversion toSiC and all of the 50 gm of Si was depleted. Radiography indicatedincomplete infiltration of the Si had occurred.

The process was repeated with a single board shaped specimen ofcarbonized redwood. The single specimen allowed more room in the furnaceboat for Si to be added, so several times more than enough was used.Similar heat treatment resulted in the specimen being bound to the boatby a pool of solidified Si. The specimen was then covered with graphiteflakes and reheated to absorb Si. The removal of excess Si wassuccessful. The converted redwood specimen was readily removed from theboat. The specimen had a green appearance underlying some gray slag onthe surface. The interior was uniformly green. Radiography indicatedthat a relatively uniform ceramic was produced.

An interior portion of the piece was scanned by XRD. The result, shownin FIG. 40, indicated only peaks for SiC. Another portion of thespecimen was then sectioned with a water cooled saw. Micrographs fromSEM revealed that the walls of the precursor wood were converted to amicrocrystalline SiC. Two images are shown in FIG. 41 and 42, whichreveal the micro-honeycomb morphology in the earlywood region of theredwood derived SiC. The higher magnification in FIG. 42 reveals thecrystallite morphology of the converted precursor cell walls.

A photograph of the specimen is shown in FIG. 43. The sectioned endreveals the darker latewood regions which were much denser. The latewoodlayers gave the specimen enough strength to allow for cutting andhandling.

Additional examples using the recessed furnace boat to hold molten Siwere successfully performed. Specimens of similar size as the boardspreviously described, but with half the width, were converted to SiC.Residual Si was required for full conversion of the specimens. Severalcarbonized wood species were converted. Also repeated was the conversionof carbonized wood specimens with nearly cubic dimensions. All specimensconverted with liquid infiltration had some residual Si in pores whichwere not closed off. FIG. 44 is a photograph of two specimens convertedto SiC. Each sample was derived from carbonized redwood and were nearlysaturated with unconverted Si. Each maintained near-net shape whenconverted. An electron micrograph of a cut section of one specimen isshown in FIG. 45. Latewood regions appear as dark bands in the image.Earlywood regions appear as a SiC honeycomb with Si filled pores, someleft unfilled.

In a further study, a converted redwood specimen was placed on a flatgraphite boat and heat treated in a nitrogen atmosphere. A furnaceschedule of 240° C./hr to 1500° C., hold 4 hrs, cool 240° C./hr, and anitrogen flow rate of 0.4 L/min were used. The specimen and boat werecoated with a white/yellow-white film which in some places took the formof small whiskers. The film of whiskers was easily scraped off thesample and boat. The specimen and whiskers were separately investigatedby XRD analysis. The specimen gave peaks for SiC, Si and Si₃N₄. Thewhiskers gave peaks for Si₃N₄ only. The diffraction patterns arepresented in FIGS. 46 and 47. The specimen was scanned several times,including after removing a layer of the surface by abrasive paper. Thestrongest peaks in all scans of the specimen matched those for SiC andSi. But even after removal of the surface layer some silicon nitride wasdetected. This example demonstrated that the residual Si could beconverted to form a ceramic/ceramic composite. A photograph of thespecimen is shown in FIG. 48.

Further methods to develop a metal matrix composite from the carbonizedwood are possible. For example, a mixture of powdered aluminum andsilicon (90/10) may be placed on a specimen of porous SiC and heated.Other alloys can also be used to produce a more refractory metal matrixcomposite.

Additional examples were performed which produced more ceramic tubesfrom bamboo. One of those, in which residual Si was present, was packedin graphite flakes and heat treated to 1500° C. to draw out the Si. Thespecimen appeared dark gray on its surface but had a green interior. Thespecimen was fragile and was easily crushed to produce green SiC fibers.Fibers up to 4 cm long were produced by crushing the converted bamboo.These fibers were also fragile and easily broken. The experiment didserve to demonstrate that ceramic fibers can be produced from naturallyfibrous plants. A photograph of the fibers and a specimen of SiC derivedfrom bamboo are shown in FIG. 49.

In another conversion experiment, a sheet of carbonized manila paper wasplaced under a specimen. Liquid Si passed into the paper and convertedit to ceramic. XRD analysis gave strong peaks for SiC. Small amounts ofresidual Si was also detected. Electron microscopy revealed themicro-crystalline morphology of the converted cellulosic fibers. Theconverted paper was brittle but very rough. Given an appropriate backingit could be produced as abrasive or refractory coatings.

To investigate the SiC-forming reaction, thermal analysis (DTA/TGA) wasperformed. In one study, powdered Si was heated in an argon atmosphereto approximately 1500° C. Melting was indicated by an endotherm justabove 1400° C. In a second study, a stoichiometric mixture of powderedcarbon (from poplar) and Si was heated. The results from these arepresented in FIG. 50. The exothermic reaction from conversion to SiCreduces the negative temperature differential found in the firstexperiment with Si only. The bi-modal endotherm of the Si was likely theresult of the powder bonding to itself before completely melting. Oncemolten, increased thermal contact to the sample cup produced a rapid andsharp reduction in measured temperature. XRD analysis of reactionproduct showed peaks for SiC and residual Si. The residual Si was alsodetected during DTA cooling as a exotherm from solidification.

Thermal analysis indicated that the reaction of Si and C to form SiCoccurs rapidly when the Si begins to melt. Therefore, when infiltratingporous carbonized wood, the pore size and volume fraction must be chosencarefully to avoid choking off when this processing approach is used.This is possible to accomplish by choosing a precursor wood specieshaving anatomical features which meet these criteria.

Other carbide ceramics can be manufactured using carbonizedlignocellulosics as precursors. Boric acid (granular) placed oncarbonized wood and heat treated to 1500° C. in an argon atmosphereproduced boron carbide (B₄C). Other processing approaches can be takento produce carbides. The sol-gel method has the advantage of beingcomposed of nano-sized particles which can be forced into carbonizedwood specimens. Colloidal solutions with varying concentrations can beused to adjust the amount of precursor left inside the naturally porousmaterial. Gas phase infiltration can also be used to convert the porouscarbonized wood to ceramic.

The current technology for the production of high performance ceramicsinvolves the preparation of high purity, submicron powders that requirespecial handling and highly controlled consolidation followed by a hightemperature sintering step. In addition, expensive machining andfinishing operations are often needed to obtain the specified dimensionsof the final component.

The processing method of the present invention demonstrates thepotential for producing advanced ceramics of net shape using wood andother naturally fibrous plants as precursors. Three fundamental aspectsof this approach give it the potential for significantly reducingprocessing costs. Inexpensive precursors are used. The need for specialhandling and sintering of powders is eliminated. Net shape processing ofthe carbonized wood eliminates the need for machining of a hard ceramic.

In accordance with this embodiment, ceramic which retains the cellularfeatures of the precursor wood may be produced. A SiC micro-honeycombceramic, for example, may be produced which has potential applicationsfor high temperature filters or as a catalyst support. These ceramicmaterials may also be suitable for high temperature structuralapplications.

Paper and fabrics of natural fibers offer design flexibility whenproducing materials using the method of carbonization of the presentinvention. Carbonized lignocellulosics retain all of the anatomicalfeatures of the precursors. In addition to the retention of features,carbonization of fabrics and papers allow for complex shapes to beproduced with some preferred orientation of the natural fibers. Thus, ifmonolithic wood samples do not allow for enough design flexibility, theuse of smaller portions of the plant formed into the desired shape canbe used. To demonstrate this aspect of the invention, severalexperiments were performed.

Several natural fiber fabrics were carbonized under controlledconditions to produce non-graphitic carbon fabrics. Cotton, muslin,linen, aida and rayon, with no coloring dyes, were all carbonized. Inone experiment, carbonized specimens were soaked in a colloidalsuspension of alumina (Nyacol AL-20). A vacuum assist was used to assureinfiltration. The specimens were allowed to dry thoroughly for days.Then heat treatment in a nitrogen atmosphere to 1500° C. was performed.The specimens were white to gray-white, and intact. XRD analysisdetected aluminum nitride (AlN) and some residual alumina (Al₂O₃). FIG.51 is a photograph of converted aida cloth comprising aluminum nitride(light) overlying a piece of carbonized aida of coarser weave (dark).The solid carbon fabric acts as a carbon source for reduction of theoxide. When performed in a nitrogen atmosphere above 1400° C. the metalis less stable than the nitride. A similar example was performed bysoaking the cellulosic cloths in the sol-gel, then carbonizing andconverting in one process. Similar results were obtained.

Other examples using carbonized fabrics and silica sol-gel give resultssimilar to those obtained using monolithic wood. Conversion productsdetected by XRD analysis are SiC and cristobalite. Other ceramics andcarbides from carbonized fabrics and papers may also be produced inaccordance with the present invention.

Another method of materials manufacture from carbonized lignocellulosicsis the capability of using lower quality forest products such as woodchips and sawdust. These can easily be bound together by polymers, suchas phenolics, to produce a precursor for carbonization. This enablesdesign flexibility similar to that gained in using papers or fabrics,the difference being the size of the lignocellulosic starting material.Large pieces with relatively thick cross-sections may be produced usinglow cost precursors. Wafers of wood can be bound with a preferredorientation (as in glue-lam products) to produce a material withanisotropic properties. Anisotropic carbon-epoxy composites or ceramicsmay thus be produced.

An example was performed to make monolithic AlN ceramics using woodsawdust as a precursor. A mixture of phenolic resin powder (Varcum29217), mixed species wood sawdust and alumina powder was pressed intopellets. A series of tests indicated that 20 wt % phenolic providedadequate bonding of the mixture. The ratio of alumina tosawdust/phenolic mix was varied from a carbon-rich ratio, to astoichiometric ratio, based on expected solid carbon yield of theorganics and a one to one (C+O→CO) reduction ratio. Pellets were curedin a hot press at 180° C. for 4 minutes. Carbonization to 600° C. in anitrogen atmosphere produced pellets which retained their shape. Furtherheat treatment for 4 hrs at 1550° C. in a nitrogen atmosphere wasperformed. The resulting pellets ranged in color from gray to white. Thedegree of whiteness decreased with increasing carbon to alumina ratio ofprecursor mix. A photograph of carbonized and converted pellets is shownin FIG. 52, with the carbonized sample on the left side and the AINsample on the right side of the photograph. XRD scans of the convertedpellets detected AlN. No residual alumina was found. Weak peaks at 26°2-theta was detected in some of the specimens indicating the presence ofsome residual solid carbon. FIG. 53 is a typical diffraction patternfrom the specimens produced. TGA experiments of the mix detected theweight loss associated with the oxide reduction at temperatures above1400° C. No differential temperature was detected from the reaction.Furthermore, mixtures of sawdust, phenolic and Si may be converted toSiC. Carbon-carbon and carbon-polymer composites can also be produced bythis processing method.

Additional processing was performed on plants naturally high ininorganics. The production of industrially important materials from suchplants is one feature of the present invention.

Two samples of scouring rush (Equisetum) were collected from differentlocations. This is a plant which contains high levels of inorganics,especially silica. Each were heat treated (separate experiments) in anargon atmosphere for 4 hrs at 1500° C. Crystal phase identification byXRD detected SiC in both samples. The results are presented in FIG. 54.One specimen gave peaks for SiC only. The other had additional peakswhich match those in the ICDD PDF for Oldhamite, a compound of calciumand sulfur. The process demonstrates the capability to process plantswhich take up inorganics from the soil. It also demonstrates thecapability of a single genus to extract different levels of inorganicsdepending upon growing conditions.

It is also possible to use plants to extract heavy metals and ions forbioremediation and then use them to manufacture a product using thecarbonization process of the present invention. Whether the product is araw material, or a ceramic monolith, would depend upon the compositionof the particular plant.

While various aspects of the invention have been discussed above, it isto be understood that various modifications, adaptations and changes maybe made without departing from the scope of the invention as set forthin the following claims.

What is claimed is:
 1. A porous ceramic-containing material comprisingceramic having a porous anisotropic cellular structure corresponding toa cellular structure of precursor wood.
 2. The porous ceramic-containingmaterial of claim 1, wherein the precursor wood comprises a single solidpiece of wood.
 3. The porous ceramic-containing material of claim 2,wherein the material has at least one dimension greater than about 1inch.
 4. The porous ceramic-containing material of claim 2, wherein thematerial comprises longitudinal-radial, longitudinal-tangential andradial-tangential planes, and extends at least about 0.5 inch in atleast two of the planes.
 5. The porous ceramic-containing material ofclaim 4, wherein the material extends at least about 0.5 inch in each ofthe planes.
 6. A ceramic-metal composite article comprising: a ceramichaving a porous anisotropic cellular structure corresponding to theanatomical structure of precursor wood; and metal at least partiallyfilling the pores of the ceramic.
 7. The ceramic-metal composite articleof claim 6, wherein the precursor wood comprises a single solid piece ofwood.
 8. The ceramic-metal composite article of claim 7, wherein thearticle has at least one dimension greater than about 1 inch.
 9. Theceramic-metal composite article of claim 7, wherein the articlecomprises longitudinal-radial, longitudinal-tangential andradial-tangential planes, and extends at least about 0.5 inch in atleast two of the planes.
 10. The ceramic-metal composite article ofclaim 9, wherein the article extends at least about 0.5 inch in each ofthe planes.
 11. The ceramic-ceramic composite article of claim 10,wherein the article extends at least about 0.5 inch in each of theplanes.
 12. A ceramic-ceramic composite article comprising: a firstceramic having a porous anisotropic cellular structure corresponding tothe anatomical structure of precursor wood; and a second ceramic atleast partially filling the pores of the first ceramic.
 13. Theceramic-ceramic composite article of claim 12, wherein the precursorwood comprises a single solid piece of wood.
 14. The ceramic-ceramiccomposite article of claim 13, wherein the article has at least onedimension greater than about 1 inch.
 15. The ceramic-ceramic compositearticle of claim 13, wherein the article comprises longitudinal-radial,longitudinal-tangential and radial-tangential planes, and extends atleast about 0.5 inch in at least two of the planes.